Substituted pyrazole derivatives

ABSTRACT

New substituted pyrazole derivatives of general formula I are described ##STR1## in which R 1 , R 2 , R 3 , R 4 , R 5  and R 6  have the meanings given in the description, processes for their preparation, as well as intermediates, and their use as herbicides.

This is a division of application Ser. No. 08/416,748, filed Apr. 12,1995.

FIELD OF THE INVENTION

This invention relates to new substituted pyrazole derivatives, theirpreparation, as well as intermediates, and their use as herbicides.

PRIOR ART

It is known that 1-phenylpyrazoles possess herbicidal activity (EP154115).

However the herbicidal activity of these compounds in not high enough orselectivity problems can occur in important crops.

The object of the present invention is to make new compounds that haveimproved biological properties over the known compounds.

It has now been found that substituted pyrazole derivatives of generalformula I ##STR2## in which R¹ is C₁ -C₄ -alkyl;

R² is C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkoxy, each of which isoptionally substituted by one or more halogen atoms, or

R¹ and R² together form the group --(CH₂)_(m) ;

R³ is hydrogen or halogen,

R⁴ is hydrogen or C₁ -C₄ -alkyl,

R⁵ is hydrogen, nitro, cyano or the groups --COOR⁷, --C(═X)NR⁸ R⁹ or--C(═X)R¹⁰,

R⁶ is hydrogen, halogen, cyano, C₁ -C₄ -alkyl, (optionally substitutedby one or more halogen or hydroxy groups), C₁ -C₄ -alkoxy, phenyl,(optionally substituted by one or more halogen, nitro, cyano, C₁ -C₄-alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄ -alkyl groups), pyrrolyl, or is aC₂ -C₈ -alkyl, C₃ -C₈ -alkenyl, C₃ -C₈ -alkynyl or C₃ -C₈ -alkoxy group,each of which is interrupted by one or more oxygen atoms, or is thegroup; ##STR3## R⁷, R⁸ and R⁹, which may be the same or different, arehydrogen or C₁ -C₄ -alkyl or

R⁸ and R⁹ together with the nitrogen to which they are attached form a 5or 6 membered saturated carbocyclic ring;

R¹⁰ is hydrogen or C₁ -C₄ -alkyl, optionally substituted by one or morehalogen atoms,

R¹¹ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl orphenyl (each of which is optionally substituted by one or more halogenatoms), C₃ -C₈ -cycloalkyl, cyanomethyl or the group R²¹ CO--;

R¹² is C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl (eachof which is optionally substituted by one or more halogen atoms), C₃ -C₈-cycloalkyl, cyanomethyl, C₁ -C₄ -alkoxy-C₁ -C₆ -alkyl, di-C₁ -C₄-alkylamino-C₁ -C₄ -alkyl, tetrahydrofurfurylmethyl, C₃ -C₆-alkynyloxy-C₁ -C₄ -alkyl, benzyl, (optionally substituted by one ormore halogen, nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄-alkyl groups), or is the group --C(═X)R²¹, --(CH₂)_(a) --(O)_(d) --R²⁸,--(CH₂)a--O--(CH₂)_(b-) R²⁸ or --(CH₂)_(a) --X--R³⁴, and when R⁵ is--C(═O)R¹⁰, and/or when R¹ is C₁ -C₄ -alkyl, R² is difluoromethoxy, R³is bromo and R⁵ is nitro or cyano, R¹² can also be hydrogen; or

R¹¹ and R¹² together with the nitrogen to which they are attached form a3, 5 or 6 membered saturated carbocyclic or aromatic ring, in which acarbon atom is optionally substituted by an oxygen atom;

R¹³ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl or C₃ -C₆ -alkynyl; orR¹³ and R¹⁴ together form the group --(CH₂)_(p) ;

R¹⁴ and R¹⁵, which may be the same or different, are C₁ -C₄ -alkyl, C₂-C₆ -alkenyl, C₃ -C₆ -alkynyl or phenyl (each of which is optionallysubstituted by one or more halogen atoms), hydrogen, C₃ -C₆ -cycloalkylor the groups --XR¹⁸ or --NR¹⁹ R²⁰ ;

R¹⁶ is hydrogen, C₁ -C₆ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl, C₁ -C₄-alkylcarbonyl, cyano-C₁ -C₃ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄-alkyl, di-C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, benzyl, C₁ -C₄-alkoxy-C₃ -C₈ -alkynyl, or the group --(CH₂)_(a) --R³³, --(CH₂)_(a)--X--R³⁰, --(CH₂)_(a) --X--(CH₂)_(b) --R³⁰ or --(CH₂)_(a) --X--(CH₂)_(b)--X--(CH₂)_(c) --R³⁰,

R¹⁷ is hydrogen, C₁ -C₄ -alkyl, C₂ -C₆ -alkenyl, C₃ -C₆ -alkynyl,cyano-C₁ -C₃ -alkyl, C₁ -C₄ -alkylcarbonyl-C₁ -C₃ -alkyl or phenyl,

R¹⁸ is C₁ -C₄ -alkyl, optionally substituted by one or more halogens;

R¹⁹ and R²⁰ which may be the same or different, are hydrogen or C₁ -C₄-alkyl;

R²¹ is C₁ -C₄ -alkyl, (optionally substituted by one or more halogens),C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl, C₃ -C₆₋cycloalkyl, phenyl, (optionally substituted by one or more halogen,nitro, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halo-C₁ -C₄ -alkylgroups), or is the group --NR³¹ R³² or --(CH₂)_(a) --(O)_(d) --R³³ ;

R²² is C₁ -C₄ -alkoxycarbonyl or carboxy,

R²³ is chloromethyl, cyanomethyl, C₃ -C₆ -cycloalkyl (optionallyinterrupted by one or more oxygen atoms), or C₁ -C₄ -alkoxycarbonyl-C₁-C₄ -alkyl,

R²⁴ is hydroxy or the group --NR²⁵ R²⁶ ;

A is --NR²⁵ R²⁶ or --S(O)_(n) --R²⁷ ;

R²⁵ and R²⁶ which may be the same or different are hydrogen or C₁ -C₄-alkyl;

R²⁷ is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl or carboxy,

R²⁸ is hydrogen, hydroxy, halogen, C₁ -C₄ -alkyl, (optionallysubstituted by one or more C₁ -C₄ -alkoxy groups), C₃ -C₆ -cycloalkyl(optionally interrupted by one or more oxygen atoms and optionallysubstituted by dimethyl), furyl, thienyl or --C(═O) R²⁹ ;

R²⁹ and R³⁰, which may be the same or different, are C₁ -C₄ -alkyl or C₁-C₄ -alkoxy;

R³¹ and R³², which may be the same or different, are C₁ -C₄ -alkyl orphenyl;

R³³ is C₃ -C₆ -cycloalkyl (optionally interrupted by one or more oxygenatoms and optionally substituted by dimethyl), furyl, thienyl or--C(═O)R²⁹ ;

R³⁴ is C₁ -C₄ -alkyl;

a, b and c are 1, 2 or 3;

d is 0 or 1;

m is 3 or 4;

p is 2 or 3; and

X is oxygen or sulfur,

possess better herbicide properties than the known compounds of relatedstructure.

Particularly active are those pyrazole derivatives as defined above, inwhich

R¹ is methyl;

R² is methylthio or difluoromethoxy (and especially difluoromethoxy); or

R¹ and R² together form the group --(CH₂)₄ ;

R³ is hydrogen, chloro or bromo;

R⁴ is hydrogen;

R⁵ is hydrogen, nitro, cyano or --C(═X) R¹⁰.

In a particularly preferred group of compounds, R⁶ is hydrogen, halogen,cyano, C₁ -C₄ -alkyl, C₁₋₄ -alkylthio or --NR¹¹ R¹², with R¹¹ and R¹²preferably being hydrogen, C₁₋₄ -alkyl or C₁₋₄ -alkoxycarbonyl.

The term "halogen" means fluorine, chlorine, bromine and iodine.

It is to be understood that the term "alkyl", "alkenyl" and "alkynyl"includes branched as well as straight chained hydrocarbon groups.

The invention also includes intermediates of general formula II ##STR4##in which R¹, R² and R³ have the meanings given in general formula I,intermediates of general formula Ii ##STR5## in which R¹ and R² have themeanings given in general formula I, intermediates of general formula Ij##STR6## in which R¹, R² and R⁵ have the meanings given in generalformula I, intermediates of general formula Ik ##STR7## in which R¹, R²and R⁶ have the meanings given in general formula I, intermediates ofgeneral formula Il ##STR8## in which R¹, R² and R³ have the meaningsgiven in general formula I, and intermediates of general formula Im##STR9## in which R¹, R², R³ and R⁶ have the meanings given in generalformula I.

The compounds of the invention of general formula I can be prepared, bya process in which

A) a compound of general formula II ##STR10## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a compoundof general formula III ##STR11## in which R⁴ and R⁵ have the meaningsgiven in general formula I and Y is C₁ -C₆ -alkoxy, hydroxy or halogen,or when R⁵ is hydrogen,

B) a compound of general formula II ##STR12## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a2-haloacrylonitrile of formula IIIa ##STR13## or with a2,3-dihalopropionitrile of formula IIIb ##STR14## in which Hal ishalogen, or when R³ is halogen,

C) a compound of general formula Ia ##STR15## in which R¹, R², R⁵, R¹¹and R¹² have the meanings given in general formula I, is reacted firstwith a halogenating agent to give a compound of formula 1b ##STR16## inwhich R¹, R², R⁵, R¹¹ and R¹² have the meanings given in general formulaI, and Hal is halogen, and then further treated to give the desiredcompound, or

when R⁵ is --C(═S)R¹⁰ and R⁶ is amino,

D) a compound of general formula Ic ##STR17## in which R¹, R², R³, R⁴and R¹⁰ have the meanings given in general formula I, is treated withLawesson's reagent, or

when R³ is --OR¹⁶ ,

E) a compound of general formula Id ##STR18## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is first diazotisedto give a compound of formula 1e ##STR19## in which R¹, R², R³, R⁴ andR⁵ have the meanings given in general formula I, and then by heating togive a compound of formula 1f ##STR20## in which R¹, R², R³, R⁴ and R⁵have the meanings given in general formula I, which is then reacted witha compound of general formula IV

    QR.sup.16                                                  (IV)

in which R¹⁶ has the meaning given in general formula I, and Q is aleaving group, or

when R⁵ is nitro and R⁶ is --SR¹⁷,

F) a compound of general formula Ig ##STR21## in which R¹, R², R³ and R⁴have the meanings given in general formula I and Hal is halogen isreacted with a nucleophile of general formula V

    .sup.⊖ SR.sup.17                                   (V)

in which R¹⁷ has the meaning given in general formula I, or when R⁵ isnitro and R⁶ is --S(O)_(n) R¹⁷, in which n is 1 or 2,

G) a compound of general formula Ih ##STR22## in which R¹, R², R³, R⁴and R¹⁷ have the meanings given in general formula I, is subjected to astepwise oxidation with m-chloroperbenzoic acid, or when R⁵ is cyano

H) a compound of general formula IIa ##STR23## in which R¹ and R² havethe meanings given in general formula I, is reacted with a compound ofgeneral formula IIIc ##STR24## in which Y is C₁ -C₄ -alkoxy, hydroxy orhalogen, or when R⁵ is nitro,

I) a compound of general formula Ii ##STR25## in which R¹ and R² havethe meanings given in general formula I, is nitrated in known manner, or

J) a compound of general formula Ij ##STR26## in which R¹, R² and R⁵have the meanings given in general formula I, is brominated in knownmanner, or when

when R⁵ is halogen,

K) a compound of general formula II ##STR27## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a compoundof general formula IIIc ##STR28## in which Y' is C₁ -C₆ -alkoxy,dimethylamino or halogen, to first give compound of formula Il ##STR29##in which R¹, R² and R³ have the meanings given in general formula I, andthis compound is then diazotised in known manner with sodium nitrite andconverted to the corresponding halide, or

L) a compound of general formula Ik ##STR30## in which R¹, R² and R⁶have the meanings given in general formula I, is treated with ahalogenating agent, or

M) a compound of general formula Im ##STR31## in which R¹, R² and R³have the meanings given in general formula I, and R⁶ is C₁ -C₄ -alkyl,(optionally substituted by one or more halogens) or is a C₂ -C₈ -alkyl,interrupted by one or more oxygens, is converted in known manner to thenitrile of general formula I, or when R⁶ is --NR¹¹ R¹²,

N) a compound of general formula In ##STR32## in which R¹, R² and R³have the meanings given in general formula I, is reacted with an aminein a solvent, or when R⁶ is --NR¹¹ R¹², in which R¹¹ is hydrogen and R¹²is C₁ -C₆ -alkyl,

O) a compound of general formula Il ##STR33## in which R¹, R² and R³have the meanings given in general formula I, is reacted with a trialkylortho ester and then reduced, or

P) a compound of general formula Io ##STR34## in which R¹, R² and R³have the meanings given in general formula I, and R¹² is C₁ -C₆ -alkylis reacted with an base and an alkylating agent or an acid chloride, orwhen R⁶ is --NR¹¹ R¹², in which R¹¹ and R¹² are C₁ -C₆ -alkyl,

Q) a compound of general formula Il ##STR35## in which R¹, R² and R³have the meanings given in general formula I, is reacted withapproximately 2 mole of base and 2 mole of a suitable alkylating agent,or

R) a compound of general formula Il ##STR36## in which R¹, R² and R³have the meanings given in general formula I, is reacted with or withouta base and a suitable acid chloride, or

S) a compound of general formula Ip ##STR37## in which R¹, R², R³ andR²¹ have the meanings given in general formula I, is reacted with a baseand a suitable alkylating agent, or

T) a compound of general formula In ##STR38## in which R¹, R² and R³have the meanings given in general formula I and R⁵ is cyano or nitro,is reacted with an oxygen, nitrogen, sulfur or carbon nucleophile, orwhen R⁶ is substituted methyl

U) a compound of general formula Iq ##STR39## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is reacted with aLewis acid, or

V) a compound of general formula Ir ##STR40## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is treated with ahalogenating agent, or

W) a compound of general formula Is ##STR41## in which R¹, R², R³, R⁴and R⁵ have the meanings given in general formula I, is reacted with anoxygen, nitrogen, sulfur or carbon nucleophile, or when R⁶ is mercapto

X) a compound of general formula It ##STR42## in which R¹, R², R³ and R⁴have the meanings given in general formula I, is treated with sodiumhydrogen sulfide, or

Y) a compound of general formula Iu ##STR43## in which R¹, R², R³ and R⁴have the meanings given in general formula I, is treated with a suitablealkylating agent, or

Z) a compound of general formula Iv ##STR44## in which R¹, R², R³ and R⁴have the meanings given general formula I, and R^(x) is C₁ -C₄ -alkyl,is oxidised stages.

The compounds of the invention of general formula I, in which R⁵ isnitro and R⁶ is halogen, can also be prepared according to the processdescribed in DE 3501323.

The compounds of the invention of general formula I, in which R⁵ is thegroup --C(O)R¹⁰ and R⁶ is amino, can also be prepared according to theprocess described in Collect. Czech. Chem. Commun. 55, 1038-48 (1990).

The compounds of the invention of general formula I, in which R⁶ is thegroup --NR¹¹ R¹², can also be prepared according to the known processesdescribed in DE 3 707 686, DE 3 543 034, EP 224 831, DE 3 543 035, JP57167972 and DE 2 747 531.

The compounds of the invention of general formula I, in which R¹⁴ is thegroup --OR¹⁸ or --NR¹⁹ R²⁰, can be prepared from compounds of generalformula I, in which R⁶ is amino according to the known processesdescribed in Chem. Soc. Rev. 4, 231-50 (1975) and J. March, AdvancedOrganic Chemistry, 1985, p. 370.

The compounds of the invention of general formula I, in which R⁵ iscyano or nitro and R⁶ is C₁ -C₄ -alkyl, can be prepared according toknown processes (J. Heterocyclic Chem. 24, 1669 (1987), ibid. 24, 739(1987).

The reactions are suitably carried out by reacting the compounds offormulae II, IIa or III in a suitable solvent at a temperature between-30° and 150° C., preferably at room temperature.

As halogenating agent there can be used for example sulfuryl chloride,sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, bromine orchlorine.

Leaving groups in process variant E are chloro or bromo.

The nitration in process variant I) is suitably carried out in knownmanner with nitric acid in acetic anhydride. The reaction temperaturelies in the region of -10° to 140° C.

The process variant J) is suitably carried out in a solvent at atemperature of -20° C. up to the boiling point of the solvent.

As brominating agent in process variant J) there can be used, forexample N-bromosuccinimide or bromine.

The reaction of compounds of general formula Il is suitably carried bythe method described in J. March, Advanced Organic Chemistry, 1985, p.647.

The process variant L) is generally carried out in a suitable solvent,preferably acetonitrile or dichloromethane, at a temperature of between-10° C. and 80° C.

Process variant M) is generally carried out according to the methoddescribed in Tetrahedron Letters, 1977, p. 1813.

Process variant O) is generally carried out according to the knownmethods (J. March, Advanced Organic Chemistry, 1985, p. 798-800 andliterature cited there).

Suitable bases for process variants P), Q), R) and S) include forexample alkali metal and alkaline earth metal hydroxides, sodiummethanolate, alkali metal hydrides, alkali metal and alkaline earthmetal carbonates, tertiary aliphatic and aromatic amines, such astriethylamine and pyridine as well as heterocyclic bases.

Process variant T) is generally carried out for example according tomethods described in J. Heterocyclic Chem. 25, 555 (1988).

The preparation can be carried out with or without a solvent. Shouldneed arise, such solvent or diluents can be used which are inert to thereactants. Examples of such solvents or diluents are aliphatic,alicyclic and aromatic hydrocarbons, each of which can be optionallychlorinated, such as for example hexane, cyclohexane, petroleum ether,naphtha, benzene, toluene, xylene, methylene chloride, chloroform,carbon tetrachloride, ethylene dichloride, trichloroethane andchlorobenzene, ethers, such as for example diethyl ether, methyl ethylether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxaneand tetrahydrofuran, ketones, such as for example acetone, methyl ethylketone, methyl isopropyl ketone and-methyl isobutyl ketone, nitriles,such as for example acetonitrile and propionitrile, alcohols, such asfor example methanol, ethanol, isopropanol, butanol, tert-butanol,tert-amyl alcohol and ethylene glycol, esters, such as for example ethylacetate and amyl acetate, amides, such as for example dimethylformamideand dimethylacetamide, sulfoxides, such as for example dimethylsulfoxide and sulfones such as for example sulfolane, bases, such as forexample pyridine and triethylamine, carboxylic acids such as for exampleacetic acid, and mineral acids such as for example sulfuric acid andhydrochloric acid.

The compounds of the invention can be worked up in conventional manner.Purification can be achieved by crystallisation or columnchromatography.

The compounds of the invention are, as a rule, colourless or slightlyyellow crystalline or liquids or substances that are highly soluble inhalogenated hydrocarbons, such as methylene chloride or chloroform,ethers, such as diethyl ether or tetrahydrofuran, alcohols, such asmethanol or ethanol, ketones, such as acetone or butanone, amides, suchas dimethylformamide, and also sulfoxides, such as dimethyl sulfoxide.

The intermediate compounds of general formula II ##STR45## in which R¹,R² and R³ have the meanings given in general formula I can be preparedin known manner (e.g. JP 62158260) from compounds of general formula VI##STR46## in which R¹, R² and R³ have the meanings given in generalformula I.

The compounds of general formula II in which R¹ and R² together form thegroup --(CH₂)_(m) -- and R³ is hydrogen, can be prepared by treating acompound of general formula IIIc ##STR47## with hydrazine with additionof a base. The compound of general formula IIIc can be prepared byreacting a compound of general formula IIId ##STR48## and a1,1-dihaloethylene.

The compounds of general formula VI, in which R¹ and R² have themeanings given in general formula I and R³ is halogen, can be preparedby reacting a compound of general formula VI in which R³ is hydrogen,with a halogenating agent.

The compounds used as starting materials for compounds of generalformula VI, are of general formula VII ##STR49## in which R¹ has themeaning given in general formula I, and can be prepared for example, bya process in which, in the case when R² is C₁ -C₄ -alkyl, optionallysubstituted by halogen,

a) a compound of general formula VIII, VIIIa or IX ##STR50## in which R²is C₁ -C₄ -alkyl, optionally substituted by halogen, is reacted with acompound of general formula X

    R.sup.1 --NHNH.sub.2                                       (X)

in which R¹ has the meaning given in general formula I, optionally inthe presence of a solvent, or

when R² is C₁ -C₄ -alkylthio, optionally substituted by one or morehalogens,

b) a compound of general formula XI ##STR51## in which R³⁵ is cyano orthe group --COOR³⁶, in which R³⁶ is C₁ -C₄ -alkyl, is reacted with acompound of general formula X, optionally in the presence of a solvent,e.g. water, to give first a compound of general formula XII ##STR52## inwhich R¹ has the meaning given in general formula I and R³⁵ has themeaning given above, which is then reacted with a compound of generalformula XIII

    R.sup.37 Q                                                 (XIII)

in which R³⁷ is C₁ -C₄ -alkyl, optionally substituted by one or morehalogens, and Q is a leaving group, and the resulting compound ofgeneral formula XIV ##STR53## is saponified and decarboxylated accordingto known literature methods (e.g. Zeitschrift fur Chemie 420, (1968)),or

c) a compound of general formula XV ##STR54## in which R³⁵ is cyano orthe group --COOR³⁶, in which R³⁶ is C₁ -C₄ -alkyl, and R³⁷ is C₁ -C₄-alkyl, optionally substituted by one or more halogens, is reacted witha compound of general formula X, optionally in the presence of asolvent, e.g. water, to give a compound of general formula XIV, or

when R² is C₁ -C₄ -alkoxy, optionally substituted by one or morehalogens

d) a compound of general formula XVI ##STR55## in which R^(L) has themeaning given in general formula I, is reacted with a compound ofgeneral formula XIII, in the presence of a base, or

h) a compound of general formula XVII ##STR56## in which R¹ has themeaning given in general formula I and Z is C₁ -C₄ -alkyl, is reacted,in the presence of a base, with a compound of general formula XIII

    R.sup.37 Q                                                 (XIII)

in which R³⁷ is C₁ -C₄ -alkyl, optionally substituted by one or morehalogens, and Q is a leaving group, and the resulting compound ofgeneral formula XVIII ##STR57## in which R¹ has the meaning given ingeneral formula I, R³⁷ is C₁ -C₄ -alkyl, optionally substituted by oneor more halogens, and Z is C₁ -C₄ -alkyl, is reacted with ammonia andthe resulting compound of general formula XIX ##STR58## in which R¹ hasthe meaning given in general formula I and R³⁷ is C₁ -C₄ -alkyl,optionally substituted by one or more halogens, is reacted with sodiumhydroxide and a halogen, or

when R³ in general formula I is halogen,

f) a compound of general formula XVIII or XIX ##STR59## in which R¹ hasthe meaning given in general formula I, R³⁷ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens, and Z is C₁ -C₄ -alkyl, is reactedwith a halogenating agent to give a compound of general formula XVIIIaand XIXb ##STR60## in which R¹, R³⁷ and Z have the meanings given ingeneral formula XVIII and XIX, or

g) a compound of general formula XIXa ##STR61## in which R¹ has themeaning given in general formula I, R³⁷ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens, and Hal is halogen, is reacted withsodium hydroxide and bromine to give a compound of general formula XX##STR62## in which R¹, R³⁷ and Hal have the meanings given in formulaXIXa, or when R¹ and R² together form a tri- or tetramethylene group

h) a compound of general formula XXI ##STR63## in which n is 2 or 3, isreacted with hydrazine and the resulting3(5)-amino-5(3)-hydroxyalkylpyrazole of general formula XXII ##STR64##in which n is 2 or 3, is reacted with hexane-2,5-dione, phthalicanhydride or tetrahydrophthalic anhydride, in a similar manner to knownliterature methods (Bull. Chem. Sec. Jp., 44, 2856-8 (1971), or EP305826), to give a compound of general formula XXIII ##STR65## in whichn is 2 or 3 and Q is an amine protecting group, such as e.g. Q₁, Q₂ orQ₃ ##STR66## and this is cyclised using the Mitsunobu variant(Synthesis, 1 (1981)), to give a compound of general formula XXIV##STR67## in which n is 2 or 3, and then in the case when Q is Q₁, thisis treated with hydroxylamine as described in J. Org. Chem., 49,1224-1227 (1984), and in the case when Q is Q₂ or Q₃, this is treatedwith hydrazine, in a similar manner to known literature methods (Org.Synthesis, Coll. Vol., 3, 148 (1955)).

The starting materials of general formula XXI can be prepared in knownmanner (Chem. Ber., 109(1), 253-60, 1976).

The compounds of general formula Ii, used as starting materials, can beprepared by decarboxylating a compound of general formula XXV ##STR68##in which R¹ and R² have the meanings given in general formula I.

The compounds of general formula XXV can be prepared by saponifying acompound of general formula XXVI ##STR69## in which R¹ and R², have themeanings given under general formula I and R⁷ is C₁ -C₄ -alkyl.

The compounds of general formula XXVI can be prepared by reacting acompound of general IIa, in which R¹ and R² have the meanings givenunder general formula I with a compound of general formula XXVII##STR70## in which R⁷ is C₁ -C₄ -alkyl and Y is C₁ -C₆ -alkoxy, hydroxyor halogen.

The intermediates of general formula Ij, can be prepared in an analogousway to process described above in which instead of the compounds ofgeneral formulae IIa and Ii the corresponding compounds of generalformula XXVIII and/or XXIX ##STR71## are used.

The intermediates of general formula Ik, can be prepared by reacting acompound of general formula IIb ##STR72## in which R¹ and R² have themeanings given in general formula IIb in an analogous way to processesdescribed above.

The intermediates of general formula Im, in which R⁶ is C₁ -C₄ -alkyl,optionally substituted by one or more halogens or C₂ -C₈ -alkyl,interrupted by one or more oxygen atoms, can be prepared converting acompound of general formula Iq ##STR73## in which R¹, R² and R³ have themeanings given in general formula I, R⁶ is C₁ -C₄ -alkyl, optionallysubstituted by one or more halogens or C₂ -C₃ -alkyl, interrupted by oneor more oxygen atoms, and R⁷ is C₁ -C₄ -alkyl, in known manner to theamide.

The compounds of general formula Iq can be prepared in known manner (J.Heterocyclic Chem 24, 1669 (1987), ibid. 24, 739 (1987)).

The preparation of the intermediates can be carried out with or withouta solvent. Should need arise, a solvent mentioned above can be used.

The named starting materials are either known in the or can be preparedin similar manner to known methods.

The compounds of the invention show a good herbicidal activity againstbroad leaved weeds and grasses. A selective use of the compounds of theinvention in various crops is possible for example in rape, beet, soyabeans, cotton, rice, barley, wheat and other cereals. Individual activesubstances are particularly suitable as selective herbicides in beet,cotton, soya, maize and cereals. However the compounds can be used forcontrol of weeds in permanent crops, such as for example forestry,ornamental trees, fruit, vine, citrus, nut, banana, coffee, tea, rubber,oil palm, cocoa, berry fruit and hop plantations.

The compounds of the invention can used for example against thefollowing plant species:

Dicotyledonous weeds of the species: Sinapis, Lepidium, Galium,Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Brassica,Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea,Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum,Rorippa, Lamium, Veronica, Abutilon, Datura, Viola, Galeopsis, Papaver,Centaurea and Chrysanthemum.

Monocotyledonous weeds of the species: Arena, Alopecurus, Echinochloa,Setaria, Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus,Cyperus, Agropyron, Sagittaria, Monocharia, Fimbristylis, Eleocharis,Ischaemum and Apera.

The rates of use vary depending on the manner of pre- and postemergentuse between 0.001 and 5 kg/ha.

The compounds of the invention can also be used as defoliants,desiccants and total herbicides.

The compounds of the invention can be used either alone or in admixturewith one another or with other active agents. Optionally, otherplant-protective agents or pesticides can be added, depending on thepurpose for the treatment. When it is desired to broaden the spectrum ofactivity, other herbicides can also be added. Herbicidally active mixingpartners suitable in this connection include for example, the activeagents listed in Weed Abstracts, vol. 40, No. 1, 1991, under the heading"Lists of common names and abbreviations employed for currently usedherbicides and plant growth regulators in Weed Abstracts".

An improvement in the intensity and speed of action can be obtained, forexample, by addition of suitable adjuvants, such as organic solvents,wetting agents and oils. Such additives may allow a decrease in thedose.

The designated active ingredients or their mixtures can suitably beused, for example, as powders, dusts, granules, solutions, emulsions orsuspensions, with the addition of liquid and/or solid carriers and/ordiluents and, optionally, binding, wetting, emulsifying and/ordispersing adjuvants.

Suitable liquid carriers are, for example aliphatic and aromatichydrocarbons, such as benzene, toluene, xylene, cyclohexanone,isophorone, dimethyl sulfoxide, dimethylformamide and other mineral-oilfractions and plant oils.

Suitable solid carriers include mineral earths, e.g. bentonite, silicagel, talcum, kaolin, attapulgite, limestone, silicic acid and plantproducts, e.g. flours.

As surface-active agents there can be used for example calciumlignosulfonate, polyoxyethylenealkylphenyl ethers, naphthalenesulfonicacids and their salts, phenolsulfonic acids and their salts,formaldehyde condensates, fatty alcohol sulfates, as well as substitutedbenzenesulfonic acids and their salts.

The percentage of the active ingredient(s) in the various preparationscan vary within wide limits. For example, the compositions can containabout 10 to 90 percent by weight active ingredients, and about 90 to 10percent by weight liquid or solid carriers, as well as, optionally up to20 percent by weight of surfactant.

The agents can be applied in customary fashion, for example with wateras the carrier in spray mixture volumes of approximately 100 to 1,000l/ha. The agents can be applied using low-volume or ultra-low-volumetechniques or in the form of so-called microgranules.

The preparation of these formulations can be carried out in knownmanner, for example by milling or mixing processes. Optionally,individual components can be mixed just before use for example by theso-called commonly used tank-mixing method.

Formulations can be prepared, for example, from the followingingredients.

    ______________________________________                                        A) Wettable Powder                                                            20     percent by weight active ingredient                                    35     percent by weight fuller's earth                                       8      percent by weight calcium lignosulfonate                               2      percent by weight sodium salt of                                              N-methyl-N-oleyltaurine                                                25     percent by weight silicic acid                                         B) Paste                                                                      45     percent by weight active indredient                                    5      percent by weight sodium aluminium silicate                            15     percent by weight cetyl polyglycol ether with 8                               mole ethylene oxide                                                    2      percent by weight spindle oil                                          10     percent by weight polyethylene glycol                                  23     percent by weight water                                                C) Emulsifiable Concentrate                                                   20     percent by weight active ingredient                                    75     percent by weight isophorone                                           5      percent by weight of a mixture of the sodium salt                             of N-methyl-N-oleyltaurine and calcium                                        lignosulfonate                                                         ______________________________________                                    

The following examples illustrate the preparation of compounds accordingto the invention.

EXAMPLE 1.04-Acetyl-5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)pyrazole

0.56 g (3 mmol)3-Chloro-2-hydrazino-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine wasdissolved in 5 ml ethanol and treated with 0.42 g (3 mmol)2-ethoxymethylen-3-oxobutyronitrile. After heating under reflux for 3hours, the mixture was concentrated and the residue purified by silicagel chromatography (hexane/ethyl acetate 1:1).

Yield: 0.75 g=89.4% of theory; mp: 153°-154° C.

EXAMPLE 1.15-Amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-thioacetylpyrazole

0.28 g (1 mmol)4-Acetyl-5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)pyrazolewas dissolved in 5 ml dimethoxyethane and treated with 0.28 (0.6 mmol)Lawesson's reagent. After heating under reflux for 2 hours withstirring, the reaction solution was poured into water and extracted withethyl acetate. The organic phase was washed with saturated aqueoussodium chloride, dried over magnesium sulfate and concentrated. Theresidue was purified by silica gel column chromatography. (Hexane/ethylacetate 1:1).

Yield: 0.21 g=71% of theory; mp: 166°-167° C.

EXAMPLE 1.2N-[1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-nitro-5-pyrazolyl]propionamide

8.72 g (29.7 mmol)N-[1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-pyrazolyl]propionamidewas suspended in 33 ml acetic acid. Under ice cooling, at 0°-5° C., 3.31g (32.5 mmol) acetic anhydride was added. 1.93 g (31 mmol) Fuming nitricacid was added dropwise. After stirring for 6 hours at room temperature,the mixture was concentrated. The residue was taken up indichloromethane, neutralised with aqueous sodium hydrogen carbonate andwashed with aqueous sodium chloride. The organic phase was dried overmagnesium sulfate and concentrated. The residue was purified by silicagel chromatography (hexane/ethyl acetate 1:1).

Yield: 6.03 g=60% of theory; mp: 46°-49° C.

EXAMPLE 2.0N-[1-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl]-2,2,2-trifluoroacetamide

0.79 g (2.1 mmol)N-[1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl]-2,2,2-trifluoroacetamidewas suspended in 35 ml dichloromethane and treated with 0.17 ml sulfurylchloride. The mixture was stirred for one hour at room temperature andconcentrated.

Yield: 0.77 g=89.5% of theory; mp: 136°-139° C.

EXAMPLE 2.1N-[1-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-nitro-5-pyrazolyl]acetamide

1.3 g (5.0 mmol)5-Amino-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole wasdissolved in 20 ml acetic acid and treated with 0.55 g (5.4 mmol) aceticanhydride. After stirring for 2 hours at room temperature the reactionsolution was cooled to 0° C. and 0.4 g (6.4 mmol) concentrated nitricacid added. After stirring for 8 hours at room temperature, the reactionmixture was poured into ice water and extracted with ethyl acetate. Theorganic phase was dried over magnesium sulfate and concentrated. Theresidue was purified by silica gel column chromatography (hexane/ethylacetate 1:1).

Yield: 1.4 g=81.5% of theory; mp: 132° C.

EXAMPLE 3.15-Amino-4-nitro-1-(4-bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole

8.3 g (0.052 mol) Bromine was added dropwise at room temperature to 13 g(0.047 mol)5-amino-4-nitro-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazoledissolved in 260 ml acetic acid and the mixture stirred for 30 minutes.It was then concentrated and the residue taken up in the ethyl acetateand shaken with 5% aqueous sodium hydrogen carbonate. The phases wereseparated and the organic phase dried over magnesium sulfate. This wasconcentrated and the residue purified by silica gel columnchromatography (hexane/ethyl acetate 3:1).

Yield: 8.3 g=49.6% of theory; mp: 148° C.

PREPARATION OF THE STARTING MATERIALS 1.5-Amino-4-nitro-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-pyrazole

15 g (0.065 mol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole was dissolvedin 60 ml acetic acid and treated with 7.35 g (0.072 mol) aceticanhydride. After stirring at room temperature for 3 hours, the reactionmixture was cooled to 10° C. 4.95 g (0.078 mol) Fuming nitric acid wasadded dropwise and the mixture treated with 8.0 g (0.078 mol) aceticanhydride. After stirring for 18 hours at room temperature, the reactionmixture was added to 500 ml ice-water. It was extracted three times withethyl acetate, the organic phases were washed with water andconcentrated. The residue was treated with 80 ml ethanol and 40 mlconcentrated hydrochloric acid. After heating for 8 hours under reflux,the ethanol was removed and the residue extracted with ethyl acetate.The concentrated ethyl acetate phases were washed with saturated aqueoussodium hydrogen carbonate, dried over magnesium sulfate andconcentrated. The residue was recrystallised from diisopropyl ether andethyl acetate.

Yield: 10 g=56% of theory; mp: 140° C.

2. 5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)pyrazole

16.5 (0.06 mol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarboxylicacid was heated at 210° C. for 5 minutes and then cooled. The congealedmelt was recrystallised from diisopropyl ether.

Yield: 12.6 g=92% of theory; mp: 106°-107° C.

3.5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarboxylicAcid

18.9 g (0.06 mol) Ethyl5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolyl-4-pyrazolecarboxylatewas dissolved in 150 ml 50% ethanol and treated with 15 ml 5% causticsoda. The mixture was heated for 2 hours at 80° C., the ethanoldistilled, the residue treated with ice-water and acidified withconcentrated hydrochloric acid. The residue was removed by suctionfiltration, washed with water and dried in vacuo at 75° C.

Yield: 16.7 g=97% of theory; mp: 173° C. (dec.)

4. Ethyl5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolyl-4-pyrazolecarboxylate

19 g (0.1 mol) 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole wasdissolved in 100 ml ethanol. 18.05 g (0.1 mol) Ethylethoxymethylenecyanoacetate was added and the mixture heated for 1.5hours at boiling. After cooling, the precipitated product was removed bysuction filtration, washed with some ethanol and dried. Yield: 18.95g=59% of theory; mp: 168°-169° C.

5. 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole

39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-1-methylpyrazole wasdissolved in 224 ml water and 450 ml concentrated hydrochloric acid. At-10° C., 18.55 g (0.27 mol) sodium nitrite in 80 ml water was addeddropwise. After stirring for 1 hour at -10° C., 137.6 g tin(II)chloride,dissolved in 180 ml concentrated hydrochloric acid, was added, dropwise,at this temperature. After a further hour stirring at -10° C., 805 ml32% caustic soda was added dropwise at this temperature. The reactionmixture was shaken 8 times with ethyl acetate, the combined organicphases washed with saturated aqueous sodium chloride, dried overmagnesium sulfate and concentrated.

Yield: 42.24 g=97.2% of theory.

EXAMPLE 3.25-Amino-1-(4-bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

5.0 g (20 mmol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrilewas dissolved in 80 ml acetic acid. At room temperature, 1.2 ml (23mmol) bromine was added, dropwise. After stirring for 15 minutes, themixture was concentrated and stirred with diisopropyl ether/propanol.The solid material was suction filtered and dried.

Yield: 5.7 g=87% of theory; mp: 160° C.

EXAMPLE 3.35-Amino-1-(3-bromo-4,5,6,7-tetrahydropyrazolo-[1,5-a]-pyridin-2-yl)-4-nitropyrazole

3.6 g (12.7 mmol)5-Amino-1-(3-bromo-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)pyrazolewas suspended in 15 ml acetic acid and treated with 1.23 ml (13.0 mmol)acetic anhydride. The mixture was stirred for 5 hours at roomtemperature. 1.5 ml (15.9 mmol) acetic anhydride was added and then,with ice-bath cooling, 0.66 ml (15.5 mmol) fuming nitric acid was added,dropwise. After stirring for 12 hours at room temperature, the mixturewas concentrated. The residue was dissolved in 30 ml ethanol and treatedwith 11.2 ml concentrated hydrochloric acid. After heating for 3 hoursunder reflux, the mixture was concentrated and the residue taken up inwater and ethyl acetate. It was made basic with 2N aqueous sodiumhydroxide and the organic phase separated. The aqueous phase wasextracted twice with ethyl acetate. The combined organic phases werewashed once with water and once with saturated aqueous sodium chloride.The organic phase was dried and concentrated. The residue wasrecrystallised from ethyl acetate.

EXAMPLE 4.11-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-diethylamino-4-pyrazolecarbonitrile

10.45 g (0.35 mol) Sodium hydride (80%) was added to 100 mltetrahydrofuran and cooled to 0° C. In a nitrogen atmosphere, asuspension of 43.6 g (0.17 mol)5-amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-pyrazolecarbonitrilein 500 ml tetrahydrofuran was added dropwise. The mixture was stirredfor 1.5 hours. Then 31.4 ml (0.38 mol) iodoethane in 20 mltetrahydrofuran was added dropwise at 15° C. After stirring for threehours at 15° C., the mixture was cooled. Water was then added dropwiseand the mixture extracted with ethyl acetate. The organic phase wasseparated, dried and concentrated. The residue was recrystallised fromethyl acetate.

Yield: 47.3 g=89.4% of theory; mp: 68°-70° C.

EXAMPLE 4.2 1-(3-Chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-(ethylmethylamino)-4-pyrazolecarbonitrile

23.3 g (88.7 mmol)5-Amino-1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-4-pyrazolecarbonitrile,202 ml (1,21 mmol) triethyl orthoformate and 10 drops trifluoroaceticacid was heated for 5 hours with removal of water in a water bath at atemperature of 150° C. The reaction solution was concentrated, theresidue was suspended in 250 ml ethanol and treated, portionwise, withcooling with 4.2 g (106.4 mmol) sodium borohydride. The mixture washeated to reflux until no more gas evolution was observed. Then themixture was concentrated and the residue carefully added to ice-water.The mixture was extracted 3 times with methylene chloride and theextracts dried. The organic phase was concentrated. 2.61 g (87.1 mmol)Sodium hydride (80%) was added to 150 ml tetrahydrofuran and at 0° C.,24.1 g (87.1 mmol) of the resulting1-(3-chloro-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridin-2-yl)-5-methylamino-4-pyrazolecarbonitrilein 500 ml tetrahydrofuran was added dropwise. After stirring for 1 hourat room temperature, 7.82 ml (95.8 mmol) iodoethane was added and themixture heated at 70° C. for 3 hours. Water was added dropwise and themixture extracted 3 times with ethyl acetate. The organic phase wasseparated, dried and concentrated. The residue was recrystallised fromethyl acetate.

Yield: 18.97 g=71% of theory; mp: 68°-69° C.

EXAMPLE 4.35-Bromo-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

5.68 g (19.7 mmol)5-Amino-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrilewas dissolved in 66.3 ml hydrobromic acid (47%) and the mixture cooledto -6° C. Under a nitrogen atmosphere, 2.36 g (34.2 mmol) sodium nitritein 5.9 ml water was added dropwise. The mixture was stirred for 15minutes at this temperature and heated to room temperature. 200 ml waterwas then added and the mixture extracted 4 times with methylenechloride. The organic phase was washed with saturated aqueous sodiumhydrogen carbonate, dried over magnesium sulfate and concentrated.

Yield: 6.94 g=99.5% of theory; mp: 78° C.

PREPARATION OF THE STARTING MATERIALS 1.5-Amino-1-(4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

5.0 g (19.7 mmol)5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrilewas dissolved in 180 ml acetonitrile and 2.65 g (19.7 mmol) sulfurylchloride added dropwise. The mixture was stirred for one hour at roomtemperature and concentrated.

Yield: 5.68 g=99.5% of theory; mp: 140°-142° C.

2.5-Amino-1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-4-pyrazolecarbonitrile

22.5 g (0.13 mol) 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole wasdissolved in 310 ml ethanol and treated with 5.4 g (0.13 mol)ethoxymethylenemalononitrile. After the mixture had been heated underreflux for one hour it was cooled. The precipitate was suction filteredand washed with a small amount of ethanol.

Yield: 19.28 g=60% of theory; mp: 141°-143° C.

3. 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole

39.8 g (0.25 mol) 3-Amino-5-difluoromethoxy-1-methylpyrazole wasdissolved in 225 ml water and 450 ml concentrated hydrochloric acid. At-10° C., 18.55 g (0.27 mol) sodium nitrite in 80 ml water was addeddropwise. After stirring for one hour at -10° C., 137.6 gtin(II)chloride, dissolved in 180 ml concentrated hydrochloric acid, wasadded dropwise at this temperature. After stirring for a further hour at-10° C., 805 ml 32% caustic soda was added dropwise at this temperatureto the reaction mixture. The mixture was shaken 8 times with ethylacetate, the combined organic phases washed with aqueous saturatedsodium chloride, dried over magnesium sulfate and concentrated.

Yield: 42.24 g=97.2% of theory.

4. 3-Amino-5-difluoromethoxy-1-methylpyrazole

71.7 g (1.79 mol) Sodium hydroxide was added to 600 ml water and themixture cooled to -5° C. At this temperature, 57.3 g (0.36 mol) brominewas added dropwise at such a rate that the temperature did not riseabove 0° C. Then 57.1 g (0.3 mol)3-carbamoyl-5-difluoromethoxy-1-methylpyrazole was added portionwise at0° C. The reaction mixture was stirred for one hour at 80° C. and thensaturated with sodium chloride. The precipitate which formed was suctionfiltered off. The filtrate was shaken 6 times with the ethyl acetate.The organic phase was dried over magnesium sulfate and concentrated. Theprecipitate which had been removed was dissolved in 500 ml water and thesolution heated to boiling point for one hour. The reaction solution wassaturated with sodium chloride and shaken 6 times with ethyl acetate.The organic phase was dried with magnesium sulfate and concentrated.

Yield: 34.2 g=70.5% of theory; mp: 57° C.

5. 3-Carbamoyl-5-difluoromethoxy-1-methylpyrazole

80.6 g (0.39 mol) 3-Methoxycarbonyl-5-difluoromethoxy-1-methylpyrazoleand 300 ml aqueous ammonia (33%) was stirred for one hour under reflux.The reaction solution was cooled, the precipitate suction filtered offand washed with water and diisopropyl ether.

Yield: 58.9 g=78.8% of theory; mp: 154° C.

6. 5-Difluoromethoxy-3-methoxycarbonyl-1-methylpyrazole

67.6 g (0.43 mol) 5-Hydroxy-3-methoxycarbonyl-1-methylpyrazole and 299.2g (2.17 mol) potassium carbonate was dissolved in 1500 mldimethylformamide and heated to 70° C. At this temperaturechlorodifluoromethane was introduced over 2 hours and the mixturestirred at 80° C. for 1.5 hours. The reaction mixture was added to waterand extracted 6 times with ethyl acetate. The combined organic phaseswere washed with saturated aqueous sodium chloride and dried overmagnesium sulfate. The reaction solution was concentrated.

Yield: 80.6 g=90.3% of theory.

7. 5-Hydroxy-3-methoxycarbonyl-1-methylpyrazole

102.3 g (0.72 mol) Dimethyl acetylenedicarboxylate was added to 1000 mlether and the mixture cooled to -5° C. in an ice-methanol bath. 33 g(0.72 mol) methylhydrazine in 100 ml ether was added dropwise at a ratethat the inner temperature did not rise above 0° C. The mixture wasstirred for one hour at 0° C., the precipitate suction filtered off,washed with ether and dried at 40° C. in vacuo. The intermediate wasimmersed in an oil-bath heated to 120° C. The reaction product wasrecrystallised from methanol.

Yield: 67.6 g=60.1% of theory; mp: 197° C.

8. 4-Chloro-5-difluoromethoxy-3-methoxycarbonyl-1-methyl-pyrazole

2.1 g (10 mmol) 5-Difluoromethoxy-3-methoxycarbonyl1-methylpyrazole,dissolved in 30 ml methylene chloride, was treated with 1.35 g (10 mmol)sulfuryl chloride and the mixture stirred at room temperature for 10minutes. It was then concentrated and the residue recrystallised fromdiisopropyl ether/ethyl acetate.

Yield: 1.8 g=74.8% of theory; mp: 51° C.

EXAMPLE 4.41-(4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrile

0.57 g (2.25 mmol)1-(5-Difluoromethoxy-1-methyl3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrilewas dissolved in 30 ml methylene chloride and at room temperature wastreated with 0.30 g (2.25 mmol) sulfuryl chloride. The mixture wasstirred for one hour and then concentrated.

Yield: 0.65 g=99.8% of theory; mp: 69°-70° C.

PREPARATION OF THE STARTING MATERIALS 1.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonitrile

A mixture of 0.79 g (2.91 mmol)1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxamide,0.46 g (5.85 mmol) pyridine and 20 ml 1,4-dioxane was cooled to 5° C.and 0.74 g (3.51 mmol) trifluoroacetic anhydride was added dropwise. Themixture was stirred for 3 hours at room temperature. It was then addedto 100 ml water and extracted 4 times with ethyl acetate. The organicphase was dried over magnesium sulfate and concentrated.

Yield: 0.74=99.8% of theory; mp: 106°-107° C.

2.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxamide

0.98 g (3.38 mmol)1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonylchloride was dissolved in 20 ml tetrahydrofuran and 50 ml aqueousammonia (33%) was added with stirring. After stirring for 3 hours atroom temperature, the mixture was concentrated to half and acidifiedwith dilute hydrochloric acid. The precipitate was suction filtered off,washed with a small amount of water and dried.

Yield: 0.27 g=73% of theory; mp: 116°-118° C.

3.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarbonylChloride

0.2 g (3.8 mmol)1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylicacid was suspended in 30 ml 1,2-dichloroethane and 1.19 g (10.0 mmol)thionyl chloride was added at room temperature, dropwise. The mixturewas heated for 1 hour under reflux and concentrated.

Yield: 0.98 g=100% of theory.

4.1-(5-Difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylicAcid

A mixture of 1.25 g (4.16 mmol) Ethyl1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate,20 ml ethanol and 0.97 ml aqueous sodium hydroxide (45%) was stirred for1 hour at 80° C. The reaction solution was concentrated to a half andacidified with hydrochloric acid (37%). The precipitate was suctionfiltered off, washed with water and dried.

Yield: 1.05 g=93% of theory; mp: 205°-207° C.

5. Ethyl1-(5-difluoromethoxy-1-methyl-3-pyrazolyl)-5-methyl-4-pyrazolecarboxylate

3.0 g (16.8 mmol) 5-Difluoromethoxy-3-hydrazino-1-methylpyrazole wasadded to 25 ml ethanol and treated dropwise with 2.96 g (16.0 mmol)ethyl dimethylaminomethylenacetate dissolved in 25 ml ethanol. Themixture was heated under reflux for 2 hours. After cooling theprecipitate was suction filtered off.

Yield: 2.52 g=53% of theory; mp: 100° C.

Further starting materials were prepared as follows:

1. 1,1,7-Trichloro-1-hepten-3-one

100 g (0.62 mol) 5-Chlorovaleroyl chloride was added dropwise to 78.53 g(0.589 mmol) aluminium chloride in 150 ml methylene chloride at roomtemperature. After stirring for 1 hour, 45 ml (0.558 mol)1,1-dichloroethylene in 25 ml methylene chloride was added dropwise.Under ice-cooling 100 ml water was added dropwise and solid materialsuction filtered on Celite. The filtrate was washed with water and theorganic phase dried and concentrated. The residue was distilled in arotary evaporator.

Yield: 112.76 g=93.8% of theory; b.p.: 125° C./0.4 mbar.

2. 2-Hydrazino-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine

261.9 ml (5.4 mol) Hydrazine hydrate was added dropwise to 116.6 g (0.54mol) 1,1,7-trichloro-1-hepten-3-one in ml 2-propanol at -2° C.(acetone/dry-ice). After stirring for 12 hours at room temperature 60.6g (1,08 mmol) potassium hydroxide was added and the mixture heated forhours under reflux. The reaction mixture was evaporated to dryness andthe residue treated with 100 ml water and 100 ml brine. It was extracted9 times with ethyl acetate and the and the organic phase washed withbrine, dried over sodium sulfate and concentrated.

Yield: 29.29 g=35.6% of theory; Yellow oil.

3. 5-Amino-4-cyano-1-(1-methyl-5-methylmercapto-3-pyrazolyl)pyrazole

A mixture of 2.0 g (13.1 mmol)3-Hydrazino-1-methyl-5-methylmercaptopyrazole and 1.8 g (14.4 mmol)ethoxymethylenemalononitrile in 25 ml ethanol was stirred for 30 minutesat room temperature and heated at boiling point for 3 hours. Thereaction mixture was concentrated and the residue purified by silica gelchromatography (hexane/ethyl acetate 1:1).

Yield 2.8 g=91% of theory; mp: 165°-166° C.

4. 3-Hydrazino-1-methyl-5-methylmercaptopyrazole

1.1 g (15.8 mmol) sodium nitrite in 4 ml water was added dropwise to 1.9g (13.1 mmol) 3-amino-1-methyl-5-methylmercaptopyrazole in 28 mlconcentrated hydrochloric acid at 0° C. and the mixture stirred for 2hours at 0° C. Then, at -30° C., a solution of 7.4 g (32.8 mmol)SnCl₂.2H₂ O in 5.5 ml concentrated hydrochloric acid was added dropwiseand the mixture stirred for 3 hours at this temperature. The reactionmixture was then made basic with 32% caustic soda and extracted withmethylene chloride. The organic phase was dried over sodium sulfate andconcentrated. 2.0 g of product was obtained which was used withoutfurther purification.

5. 3-Amino-1-methyl-5-methylmercaptopyrazole

5.55 g (33.0 mmol) 3-amino-4-cyano-1-methyl-5-methylmercaptopyrazoleheated with 50 ml 32% caustic soda at boiling for 24 hours. The reactionmixture was cooled, made slightly acidic with aqueous sodium hydrogenphosphate, heated for 8 hours at 50° C. and extracted with ethylacetate. The organic phase was dried over sodium sulfate, concentratedand the residue purified by silica gel chromatography (hexane/ethylacetate 1:1).

Yield: 19 g=398% of theory; mp: 164°-166° C.

6. 3-Amino-4-Cyano-1-methyl-5-methylmercaptopyrazole

9.63 g (56.6 mmol) [Bis(methylmercapto)methylene]malononitrile wassuspended in 50 ml water and treated with 3.7 ml (67.9 mmol)methylhydrazine. The mixture was heated at boiling for 1 hour, thereaction solution cooled, the precipitate suction filtered andrecrystallised from ethanol.

Yield: 6.5 g=68.% of theory; mp: 120°-121° C.

7.5-Amino-1-(4,5,6,7-tetrahydropyrazolo-[1.5-a]pyridin-2-yl)-4-pyrazolecarboxylicAcid and 2-Hydrazino-4,5,6,7-tetrahydro-pyrazolo[1,5-a]pyridine

These were prepared according to known methods as follows:

a) 2-Amino-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine

A solution of 8.19 g (146 mmol) potassium hydroxide in 122 ml water and122 ml ethanol was added to 19.19 g (292 mmol) hydroxylaminehydrochloride in 200 ml ethanol. The mixture was stirred for 15 minutes,12.5 g (58 mmol)2-(2,5-dimethyl-1-pyrrolyl)-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridineadded and the mixture heated under reflux for 30 hours. After distillingthe ethanol, the mixture was treated with ethyl acetate, solid materialfiltered off, the aqueous phase saturated with sodium chloride andextracted with ethyl acetate. The organic phase was washed withsaturated aqueous sodium chloride, dried over sodium sulfate andconcentrated. The crude product was purified by silica gelchromatography (ethyl acetate/methanol).

Yield: 6.12 g=7.7% of theory; ¹ H NMR (CDCl₃, 300 MHz): δ=1.75-1.85(m,2H), 1.95-2,05(m,2H) 2.68(t,2H,J=7.5 Hz), 3.5(s(wide),2H),3.92(t,2H,J=7.5 Hz), 5.33 (s,1H).

b) 2-(2,5-Dimethyl-1-pyrrolyl)-4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine

16 g (92 mmol) diethyl azodicarboxylate was added dropwise to 19.7 g (84mmol) 3(5)-(4-hydroxybutyl)-5(3)-(2,5-dimethyl-1-pyrrolyl)pyrazole and22.1 g (84 mmol) triphenylphosphine in 300 ml tetrahydrofuran under icecooling. The mixture was stirred for 4 hours at room temperature. It wasthen concentrated and the residue purified by silica gel chromatography(hexane/ethyl acetate).

Yield: 14.27 g=79% of theory

n_(D) ²⁰ : 1.5630

c) 3(5)-(4-Hydroxybutyl)-5(3)-(2,5-dimethyl-1-pyrrolyl)pyrazole

A mixture of 18 g (116 mmol) 3(5)-amino-5(3)-(hydroxybutyl)pyrazole,14.6 g (128 mmol) 2,5-hexanedione and 3.2 ml acetic acid in 100 mltoluene was heated under reflux with removal of water for 8 hours. Theresulting precipitate was suction filtered, washed with toluene anddried.

Yield: 19.7 g=72% of theory

mp: 147°-148° C.

d) 3(5)-Amino-5(3)-(hydroxybutyl)pyrazole

4,8 ml Hydrazine monohydrate was added to a solution 12.3 g (0.1 mol)tetrahydro-2H-pyran-2-ylidenacetonitrile in 100 ml toluene at roomtemperature and the mixture heated under reflux for 5 hours. A darkyellow oil separated. The reaction mixture was concentrated and theresidue purified by silica gel chromatography (ethyl acetate/methanol).

Yield: 11 g=71% of theory

In a similar manner to that described in the previous Examples, thefollowing compounds were prepared.

    __________________________________________________________________________    General formula                                                                ##STR74##                                                                    Compound                       Physical Constant                              No.   R.sup.5  R.sup.6         mp [°C.]                                                                         n.sub.D.sup.20                       __________________________________________________________________________    1.3   H        H               80-82                                          1.4   CN       H               120-121                                        1.5   H        NHCOC.sub.2 H.sub.5                                                                           149-151                                        1.6   CN       NHCH.sub.3      174-175                                        1.7   CN       N(CH.sub.3).sub.2                                                                             138-139                                        1.8   CN       N(C.sub.2 H.sub.5).sub.2  1.5432                               1.9   CN       NHCOCH.sub.2 Cl 209-211                                        1.10  CN       N(CH.sub.3)COCH.sub.2 Cl                                                                      109-110                                        1.11  CN                                                                                      ##STR75##      131-132                                        1.12  NO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                                      55-57                                          1.13  NO.sub.2 NHCH.sub.3      184-185                                        1.14  CN       Cl              176-177                                        1.15  CN       Br              196-198                                        1.16  NO.sub.2 Cl                                                             1.17  NO.sub.2 Br                                                             1.18  CN       CH.sub.3        168-171                                        1.19  CN       C.sub.2 H.sub.5                                                1.20  CN       C.sub.3 H.sub.7                                                1.21  NO.sub.2 CH.sub.3                                                       1.22  NO.sub.2 C.sub.2 H.sub.5                                                1.23  NO.sub.2 C.sub.3 H.sub.7                                                1.24  CN       OCH.sub.3                                                      1.25  CN       OC.sub.2 H.sub.5                                               1.26  NO.sub.2 OCH.sub.3                                                      1.27  NO.sub.2 OC.sub.2 H.sub.5                                               1.28  NO.sub.2 OCH(CH.sub.3)CO.sub.2 CH.sub.3                                 1.29  NO.sub.2 OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                          1.30  NO.sub.2 SCH.sub.3                                                      1.31  NO.sub.2 SOCH.sub.3                                                     1.32  NO.sub.2 SO.sub.2 CH.sub.3                                              1.33  NO.sub.2 SC.sub.2 H.sub.5                                               1.34  CN       SCH.sub.2 COOEt                                                1.35  NO.sub.2 SCH.sub.2 COOEt                                                1.36  CN       NHCO(CH.sub.2).sub.2 Cl                                                                       149-150                                        1.37  CN       NHCO(CH.sub.2).sub.3 Cl                                                                       119-121                                        __________________________________________________________________________    General formula                                                                ##STR76##                                                                    Compound                                Physical Constant                     No.   R.sup.1                                                                           R.sup.2                                                                              R.sup.3                                                                          R.sup.5                                                                            R.sup.6        mp [°C.]                                                                     n.sub.D.sup.20                  __________________________________________________________________________    2.2   CH.sub.3                                                                          OCH.sub.3                                                                            Cl NO.sub.2                                                                           NHCOCH.sub.3   46-48                                 2.3   CH.sub.3                                                                          OCHF.sub.2                                                                           H  H    NHCOCF.sub.3   67-70                                 2.4   CH.sub.3                                                                          OCHF.sub.2                                                                           H  H    N(CH.sub.3)COCH.sub.3                                                                        66                                    2.5   CH.sub.3                                                                          OCHF.sub.2                                                                           H  NO.sub.2                                                                           NHCOCH.sub.3   115-116                               2.6   CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCOCH.sub.3   106                                   2.7   CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCOC.sub.2 H.sub.5                                                                          114-119                               2.8   CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCOC.sub.3 H.sub.7                                                                          80-84                                 2.9   CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCOCH.sub.2 Cl                                                                              111-115                               2.10  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H                                                                                   ##STR77##     152-156                               2.11  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCOC.sub.2 H.sub.5                                                                          109-110                               2.12  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCOC.sub.3 H.sub.7                                                                          92-96                                 2.13  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCOCH.sub.2 Cl                                                                              118-120                               2.14  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                            ##STR78##     194-196                               2.15  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCH.sub.3     102-105                               2.16  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           N(CH.sub.3).sub.2    1.5564                          2.17  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                           NHCOCH.sub.3   162 (dec)                             2.18  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                           NHCOC.sub.3 H.sub.7                                                                          58-61                                 2.19  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                            ##STR79##     168 (dec)                             2.20  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCO.sub.2 C.sub.2 H.sub.5                                                                   144-146                               2.21  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCONH.sub.2                                         2.22  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCONHCH.sub.3                                       2.23  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H    NHCON(CH.sub.3).sub.2                                2.24  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCO.sub.2 C.sub.2 H.sub.5                                                                         1.5337                          2.25  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCONH.sub.2                                         2.26  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCONHCH.sub.3                                       2.27  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           NHCON(CH.sub.3).sub.2                                2.28  CH.sub.2).sub.4                                                                          Cl NO.sub.2                                                                           NHCO.sub.2 C.sub.2 H.sub.5                           2.29  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                           NHCONH.sub.2                                         2.30  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                           NHCONHCH.sub.3                                       2.31  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                           NHCON(CH.sub.3).sub.2                                2.32  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           OCH.sub.3                                            2.33  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           OC.sub.2 H.sub.5                                     2.34  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                2.35  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           SCH.sub.3                                            2.36  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           SOCH.sub.3                                           2.37  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                           SO.sub.2 CH.sub.3                                    2.38  (CH.sub.2).sub.4                                                                         Cl NO.sub.2                                                                           NHCOCF.sub.3   56-60                                 2.39  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                            ##STR80##     44-48                                 2.40  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                            ##STR81##           1.572                           2.41  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl NO.sub.2                                                                            ##STR82##     47-51                                 2.42  CH.sub.3                                                                          OCHF.sub.2                                                                           Cl H                                                                                   ##STR83##     122-124                               __________________________________________________________________________    General formula                                                                ##STR84##                                                                    Example                      Physical Constant                                No.   R.sup.3                                                                             R.sup.6          mp [°C.]                                                                        n.sub.D                                 __________________________________________________________________________    2.43  Cl    CH.sub.2 OCH.sub.2 CO.sub.2 Me                                                                          1.51438                                 2.44  Cl                                                                                   ##STR85##                1.50800                                 2.45  Cl                                                                                   ##STR86##                1.51254                                 2.46  Cl    CH.sub.2 SCH.sub.3        1.54268                                 2.47  Cl    CH.sub.2 SEt              1.53566                                 2.48  Cl                                                                                   ##STR87##       74                                               2.49  Cl    CH.sub.2 SCH.sub.2 CO.sub.2 Et                                                                          1.52740                                 2.50  Cl    CH.sub.2 NH.sub.2         1.53932                                 2.51  Cl    CH.sub.2 NHMe                                                     2.52  Cl    CH.sub.2 NHEt                                                     2.53  Cl                                                                                   ##STR88##                1.51362                                 2.54  Cl    CH.sub.2 NMe.sub.2                                                2.55  Cl    CH.sub.2 NEt.sub.2                                                2.56  Cl    CH.sub.2 N prop.sub.2                                             2.57  Cl    CH.sub.2 OCH.sub.2 Cl                                             2.58  Cl    CH.sub.2 OCH.sub.2 CN                                             2.59  Cl    CH.sub.2 OCH.sub.2CCH                                             2.60  Cl                                                                                   ##STR89##                                                        2.61  Cl                                                                                   ##STR90##                                                        2.62  Cl    CH.sub.2 OCH.sub.2 CO.sub.2 Et                                    2.63  Cl                                                                                   ##STR91##                                                        2.64  Cl                                                                                   ##STR92##                                                        4.6   Cl    CH.sub.3         69-70                                            4.7   Br    CH.sub.3         76-78                                            4.8   Cl    CF.sub.3         90-93                                            4.9   Br    CF.sub.3         83-86                                            4.10  Cl    C.sub.2 H5       74-76                                            4.11  Cl    C(CH.sub.3).sub.3                                                                              57-60                                            4.12  Cl    CH.sub.2 OCH.sub.3        1.50852 (20° C.)                 4.13  Br    CH.sub.2 OCH.sub.3        1.52580                                 4.14  Cl                                                                                   ##STR93##       118-122                                          4.15  Cl    CH.sub.2 OH      64                                               4.16  Cl    CH.sub.2 Cl      54                                               4.17  Cl    CH.sub.2 Br      52                                               4.18  Cl    CH.sub.2 OEt     67                                               4.19  Cl    CH.sub.2 Oprop   48                                               4.20  Cl                                                                                   ##STR94##                1.50778 (20° C.)                 4.21  Cl    CH.sub.2 O(CH.sub.2).sub.3 CH.sub.3                                                                     1.50450(20° C.)                  __________________________________________________________________________    General formula                                                                ##STR95##                                                                    Example                        Physical Constant                              No.   R.sup.1                                                                             R.sup.2 R.sup.3                                                                            R.sup.6                                                                             mp.: [°C.]                                                                     n.sub.D                                __________________________________________________________________________    4.22  CH.sub.2).sub.4                                                                             Br   Br    204-205                                        4.23  CH.sub.3                                                                            OCHF.sub.2                                                                            Cl   Br    71-74                                          4.24  CH.sub.3                                                                            OCHF.sub.2                                                                            Cl   Cl            1.54046 (20.2° C.)              4.25  CH.sub.3                                                                            OCHF.sub.2                                                                            Br   Br    96-97                                          __________________________________________________________________________    General formula                                                                ##STR96##                                                                    Example                     Physical Constant                                 No.   R.sup.3                                                                            R.sup.6          mp: [°C.]                                                                        n.sub.D                                 __________________________________________________________________________    4.26  Cl   CF.sub.3         109-110                                           4.27  Cl   C.sub.2 H.sub.5  130-131                                           4.28  Cl   C.sub.2 F.sub.5  135.5-136                                         4.29  Cl   C.sub.3 H.sub.7  62-63                                             4.30  Cl   CH(CH.sub.3).sub.2                                                                             107-108                                           4.31  Cl   Ph               153-154                                           4.32  Cl   CH.sub.2 OCH.sub.3                                                                             84-85                                             4.33  Br   CH.sub.2 OCH.sub.3                                                                             80-83                                             4.34  Cl   CH.sub.2 OC.sub.2 H.sub.5                                                                      73-74                                             4.35  Cl   CH.sub.2 OC.sub.3 H.sub.7                                                                      88-89                                             4.36  Cl   CH.sub.2 OCH(CH.sub.3).sub.2                                                                             1.5440 (20.1° C.)                4.37  Cl   CH.sub.2 OH      106-107                                           4.38  Cl   CH.sub.2 Br      128-129                                           4.39  Cl   CH.sub.2 OCH.sub.2 CCH     1.5591 (21.2° C.)                4.40  Cl   CH.sub.2 OCH.sub.2 CHCH.sub.2                                                                  100.5-102                                         4.41  Cl   CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    1.5492 (20.2° C.)                4.42  Cl   CH.sub.2 OCOCH.sub.3                                                                           102.5-103                                         4.43  Cl   CH.sub.2 OCH.sub.2 COOH                                                                        108-110                                           4.44  Cl   CH.sub.2 OCH.sub.2 COOCH.sub.3                                                                           1.5376 (20° C.)                  4.45  Cl                                                                                  ##STR97##                 1.5462 (20.1° C.)                4.46  Cl                                                                                  ##STR98##                 1.5424 (21° C.)                  4.47  Cl                                                                                  ##STR99##                 1.5500 (20° C.)                  4.48  Cl                                                                                  ##STR100##                1.5481 (20.2° C.)                4.49  Cl   CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                                        1.5377 (20° C.)                  4.50  Cl   CH.sub.2 SCH.sub.3                                                                             100-101                                           4.51  Cl   CH.sub.2 SO.sub.2 CH.sub.3                                                                     139.5-141                                         4.52  Cl   CH.sub.2 SOCH.sub.3        1.5716 (20.4° C.)                4.53  Cl   CH.sub.2 SCOOH   120                                               4.54  Cl   CH.sub.2 SCH.sub.2 COOC.sub.2 H.sub.5                                                                    1.5641 (20° C.)                  4.55  Cl   COOH             184                                               4.56  Cl   CON(C.sub.2 H.sub.5).sub.2                                                                     126.5-128                                         4.57  Cl   NHC.sub.3 H.sub.7                                                                              137                                               4.58  Cl   NHCH(CH.sub.3).sub.2                                                                           114                                               4.59  Cl   NH(CH.sub.2CHCH.sub.2)                                                                         125                                               4.60  Cl   NHC.sub.4 H.sub.9                                                                              118                                               4.61  Cl   NH[CH(CH.sub.3)CH.sub.2 CH.sub.3 ]                                                             106                                               4.62  Cl   NH[CH(CH.sub.3)CH(CH.sub.3).sub.2 ]                                                            89-92                                             4.63  Cl   NHCH.sub.2 CH.sub.2 OCH.sub.3                                                                  129                                               4.64  Cl   NHCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           111-112                                           4.65  Cl   NHCH(CH.sub.3)CH.sub.2 OCH.sub.3                                                               105-106                                           4.66  Cl   NHCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                          131-132                                           4.67  Cl   N(CH.sub.3)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                           1.5621 (20° C.)                  4.68  Cl   NHCH.sub.2 Ph    116                                               4.69  Cl                                                                                  ##STR101##      122-123                                           4.70  Br   N(CH.sub.3)C.sub.2 H.sub.5                                                                     74-76                                             4.71  Br   N(CH.sub.3)C.sub.3 H.sub.7                                                                     93-95                                             4.72  Cl   N(CH.sub.3)CH(CH.sub.3).sub.2                                                                   74                                               4.73  Cl   N(CH.sub.3)CH.sub.2CCH                                                                          91                                               4.74  Br   N(CH.sub.3)CH.sub.2CCH                                                                         112-114                                           4.75  Cl   N(C.sub.2 H.sub.5)CH.sub.2CCH.sub.2                                                             75                                               4.76  Cl   N(C.sub.2 H.sub.5)CH.sub.2CCH                                                                            1.5624 (21.5° C.)                4.77  Cl   N(C.sub.3 H.sub.7).sub.2   1.5468 (23.8° C.)                4.78  Cl                                                                                  ##STR102##      156                                               4.79  Cl                                                                                  ##STR103##       84                                               4.80  Cl                                                                                  ##STR104##      107                                               4.81  Cl   CN               123                                               4.82  Cl   N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                    1.5559 (20° C.)                  4.83  Cl   N(CH.sub.2CHCH.sub.2).sub.2                                                                     79                                               4.84  Cl                                                                                  ##STR105##      145                                               4.85  Cl   NHCH.sub.2CCH    145                                               4.86  Cl   NHCH(C.sub.2 H.sub.5).sub.2                                                                     96                                               4.87  Cl                                                                                  ##STR106##      139-142                                           4.88  Cl                                                                                  ##STR107##      141                                               4.89  Cl   NHCH.sub.2 CH.sub.2 N(C.sub.2 H.sub.5).sub.2                                                   78-80                                             4.90  Cl   NHCH.sub.2 CH.sub.2 OH                                                                         138                                               4.91  Cl   NHCH.sub.2 CH.sub.2 OCOCH.sub.3                                                                 99                                               4.92  Cl   NHCH.sub.2 CH.sub.2 Cl                                                                         158                                               4.93  Cl   NH(CH.sub.2).sub.3 OCH.sub.3                                                                   112                                               4.94  Cl   NHCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH                                                      82-84                                             4.95  Cl   NHCH.sub.2 CH(OCH.sub.3).sub.2                                                                 127-129                                           4.96  Cl   NHCH(CH.sub.3)CH(OCH.sub.3).sub.2                                                              151                                               4.97  Cl   NHCH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                          111-113                                           4.98  Cl                                                                                  ##STR108##      115-117                                           4.99  Cl                                                                                  ##STR109##      121-123                                           4.100 Cl                                                                                  ##STR110##      149-151                                           4.101 Cl                                                                                  ##STR111##      114.5-117                                         4.102 Cl   NHCH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                           113-115                                           4.103 Cl                                                                                  ##STR112##      170                                               4.104 Cl                                                                                  ##STR113##      129-131                                           4.105 Cl   NHCH.sub.2 COOC.sub.2 H.sub.5                                                                  162                                               4.106 Cl                                                                                  ##STR114##                                                        4.107 Cl                                                                                  ##STR115##                                                        4.108 Cl                                                                                  ##STR116##                                                        4.109 Cl                                                                                  ##STR117##                                                        4.110 Cl                                                                                  ##STR118##                                                        4.111 Cl                                                                                  ##STR119##                                                        4.112 Cl                                                                                  ##STR120##                                                        __________________________________________________________________________    General formula                                                                ##STR121##                                                                   Example                    Physical Constant                                  No.   R.sup.3                                                                              R.sup.6       mp: [°C.]                                                                        n.sub.D                                  __________________________________________________________________________    4.113 Cl     NHC.sub.3 H.sub.7                                                                           80                                                 4.114 Cl                                                                                    ##STR122##   77                                                 4.115 Cl     NH(CH.sub.2).sub.2 OCH.sub.3                                                                78-79                                              4.116 Cl     N(CH.sub.3)C.sub.2 H.sub.5                                                                            1.52076 (20° C.)                  4.117 Cl     N(C.sub.2 H.sub.5).sub.2                                                                              1.49924 (20° C.)                  4.118 Cl     N(CH.sub.3)CH(CH.sub.3).sub.2                                                                         1.51528 (20° C.)                  4.119 Br     N(CH.sub.3)CH(CH.sub.3).sub.2                                                                         1.51258 (20.3° C.)                4.120 Cl     N(C.sub.2 H.sub.5)CH(CH.sub.3).sub.2                                                        52                                                 4.121 Cl     N(C.sub.3 H.sub.7).sub.2                                                                              1.49338 (20° C.)                  4.122 Cl                                                                                    ##STR123##   100-102                                            4.123 Br                                                                                    ##STR124##   70-72                                              4.124 Cl                                                                                    ##STR125##             1.53388 (21.6° C.)                __________________________________________________________________________    General formula                                                                ##STR126##                                                                   Example                            Physical Constant                          No.   R.sup.1                                                                          R.sup.2                                                                            R.sup.3                                                                         R.sup.6            mp: [°C.]                                                                    n.sub.D                              __________________________________________________________________________    4.125 (CH.sub.2).sub.4                                                                      Cl                                                                              NHC.sub.2 H.sub.5  136                                        4.126 CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              NHCH.sub.3         147-148                                    4.127 CH.sub.3                                                                         OCHF.sub.2                                                                         Br                                                                              NHCH.sub.3         150-152                                    4.128 CH.sub.3                                                                         OCHF.sub.2                                                                         Br                                                                              NHC.sub.2 H.sub.5   96                                        4.129 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR127##        133                                        4.130 (CH.sub.2).sub.4                                                                      Cl                                                                              NHCH.sub.2 CN      133                                        4.131 (CH.sub.2).sub.4                                                                      Cl                                                                              NHCH.sub.2CCCH.sub.3                                                                             171.5-173.5                                4.132 (CH.sub.2).sub.4                                                                      Cl                                                                              NHCH.sub.2 CCCH.sub.3                                         4.133 (CH.sub.2).sub.4                                                                      Cl                                                                              NHCH.sub.2CCC.sub.2 H.sub.5                                   4.134 (CH.sub.2).sub.4                                                                      Cl                                                                              NHCH.sub.2CCCH.sub.2OCH.sub.3                                 4.135 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)C.sub.2 H.sub.5                                                                        69                                        4.136 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)C.sub.3 H.sub.7                                                                        89                                        4.137 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)C.sub.4 H.sub.9                                                                        72                                        4.138 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH(CH.sub.3)C.sub.2 H.sub.5                                                            68                                        4.139 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH(CH.sub.3)CH(CH.sub.3).sub.2                                                         70                                        4.140 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2 CH.sub.2 OCH.sub.3                                                            80                                        4.141 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)C.sub.3 H.sub.7                                                                 92                                        4.142 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)C.sub.4 H.sub.9                                                                      1.5471 (22.9° C.)             4.143 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)C.sub.2 H.sub.5                                                    115                                        4.144 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)CH(CH.sub.3).sub.2                                                 130-133                                    4.145 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OCH.sub.3                                                     58                                        4.146 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 Ph                                                                    110                                        4.147 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                          1.5559 (20° C.)               4.148 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                   1.5484 (20° C.)               4.149 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.3 H.sub.7)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                   1.5452 (20° C.)               4.150 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.2CCH)CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       1.55688 (20° C.)              4.151 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                              1.55644 (20° C.)              4.152 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                 94-95                                      4.153 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.2CCH)CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                     124-126                                    4.154 CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH.sub.2 OCH.sub.3                                                          1.51744 (19.9° C.)            4.155 CH.sub.3                                                                         OCHF.sub.2                                                                         Cl                                                                              N(CH.sub.2CCH)CH.sub.2 CH.sub.2 OCH.sub.3                                                              1.51376 (20° C.)              4.156 (CH.sub.2).sub.4                                                                      Cl                                                                              NH(CH.sub.2CCH)    145                                        4.157 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH(CH.sub.3)C.sub.2 H.sub.5)CH.sub.2CCH                                                        142                                        4.158 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR128##        108                                        4.159 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3)CH.sub.3                                                           106                                        4.160 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH(CH.sub.3).sub.2                                                             106                                        4.161 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.2CCH)CH(CH.sub.3)C.sub.2 H.sub.5                                                        142                                        4.162 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2 Ph                                                                           108                                        4.163 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH(C.sub.2 H.sub.5).sub.2                                                             110                                        4.164 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2 CH(OCH.sub.3).sub.2                                                           71                                        4.165 (CH.sub.2).sub.4                                                                      Cl                                                                              N(C.sub.2 H.sub.5)CH.sub.2 CH(OCH.sub.3).sub.2                                                         1.5459 (20° C.)               4.166 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.2CCH)CH.sub.2 CH(OCH.sub.3).sub.2                                                       111-113                                    4.167 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR129##        97-99                                      4.168 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR130##        169-171                                    4.169 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR131##        140-142                                    4.170 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                          1.5855 (22.4° C.)             4.171 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2CCCH.sub.3                                 4.172 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2CCC.sub.2 H.sub.5                          4.173 (CH.sub.2).sub.4                                                                      Cl                                                                              N(CH.sub.3)CH.sub.2CCCH.sub.2OCH.sub.3                        4.174 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR132##                                                   4.175 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR133##                                                   4.176 (CH.sub.2).sub.4                                                                      Cl                                                                               ##STR134##                                                   __________________________________________________________________________    General formula                                                                ##STR135##                                                                   Example                       Physical Constant                               No.   R.sup.3                                                                             R.sup.6           mp: [°C.]                                                                      n.sub.D                                 __________________________________________________________________________    4.177 Br    N(C.sub.2 H.sub.5).sub.2                                                                        71-72                                           4.178 Cl    N(CH.sub.2CCH).sub.2      1.5739 (22.8° C.)                4.179 Cl    N(CH.sub.2 CO.sub.2 C.sub.2 H.sub.5).sub.2                                                              1.5427 (20° C.)                  4.180 Cl                                                                                   ##STR136##       108                                             4.181 Cl    N(CH.sub.2CCCH.sub.3).sub.2                                       4.182 Cl    N(CH.sub.2CCC.sub.2 H.sub.5).sub.2                                4.183 Cl    N(CH.sub.2CCCH.sub.2 OCH.sub.3).sub.2                             4.184 Cl    NHCOCH.sub.3      123                                             4.185 Cl    NHCOCF.sub.3      178                                             4.186 Cl    NHCOCCl.sub.3     224                                             4.187 Cl    NHCOC.sub.2 H.sub.5                                                                             162                                             4.188 Cl    NHCOC.sub.3 H.sub.7                                                                             152                                             4.189 Br    NHCOC.sub.3 H.sub.7                                                                             148-150                                         4.190 Cl                                                                                   ##STR137##       171                                             4.191 Cl    NHCOC.sub.4 H.sub.9                                                                             103                                             4.192 Cl                                                                                   ##STR138##       252                                             4.193 Cl    NHCOCH.sub.2 OCH.sub.3                                                                          201-203                                         4.194 Cl                                                                                   ##STR139##       185-187                                         4.195 Cl                                                                                   ##STR140##       165                                             4.196 Cl                                                                                   ##STR141##       151                                             4.197 Cl                                                                                   ##STR142##        75                                             4.198 Cl                                                                                   ##STR143##       185                                             4.199 Cl    NHCON(CH.sub.3).sub.2                                                                           168                                             4.200 Cl    NHCSN(CH.sub.3).sub.2                                                                           170                                             4.201 Cl    NHCON(CH.sub.3)Ph 62-64                                           __________________________________________________________________________    General formula                                                                ##STR144##                                                                   Example                         Physical Constant                             No.   R.sup.3                                                                              R.sup.6            mp: [°C.]                                                                        n.sub.D                             __________________________________________________________________________    4.202 Cl                                                                                    ##STR145##        125                                           4.203 Cl     NHCH.sub.2 CO.sub.2 Et                                                                           107-109                                       4.204 Cl                                                                                    ##STR146##        111-113                                       4.205 Cl     N(Et)COCH.sub.3    78-80                                         4.206 Cl     N(Et)COCH.sub.2 Cl           1.53412                             4.207 Cl                                                                                    ##STR147##        85-87                                         4.208 Cl     N(Et)COEt                    1.51132                             4.209 Cl                                                                                    ##STR148##                  1.51214                             4.210 Cl                                                                                    ##STR149##                  1.52582                             4.211 Cl     N(CH.sub.2 CO.sub.2 Me)COEt                                                                      87-90                                         4.212 Br     NHCOEt             120-122                                       4.213 Br     NHCOnbutyl         100-104                                       4.214 Br                                                                                    ##STR150##        103                                           4.215 Br     N(COEt).sub.2      105-107                                       4.216 Cl     NHCOCH.sub.3       116-118                                       4.217 Cl     NHCOCH.sub.2 Cl    135-137                                       4.218 Cl     NHCOCF.sub.3       134-137                                       4.219 Cl     NHCOC.sub.2 H.sub.5                                                                              126-128                                       4.220 Br     NHCOC.sub.3 H.sub.7                                                                              141-144                                       4.221 Cl     NHCOC.sub.3 H.sub.7                                                                              140-143                                       4.222 Cl                                                                                    ##STR151##         96-100                                       4.223 Cl     N(COCH.sub.3).sub.2                                                                              117-119                                       4.224 Cl     N(COC.sub.2 H.sub.5).sub.2                                                                       93-95                                         4.225 Cl     N(COC.sub.3 H.sub.7).sub.2                                                                       73-76                                         __________________________________________________________________________    General formula                                                                ##STR152##                                                                   Example                        Physical Constant                              No.   R.sup.3                                                                            R.sup.6             mp: [°C.]                                                                      n.sub.D                                __________________________________________________________________________    4.226 Cl   N(CH.sub.3)COCH.sub.3                                                                             121                                            4.227 Cl   N(C.sub.2 H.sub.5)COCH.sub.3                                                                       79                                            4.228 Cl   N(C.sub.3 H.sub.7)COCH.sub.3                                                                       85                                            4.229 Cl   (CH.sub.2CCH)COCH.sub.3                                                                            06                                            4.230 Cl   N(CH.sub.2 CH.sub.2 OCH.sub.3)COCH.sub.3                                                          128                                            4.231 Cl   N(CH.sub.2 Ph)COCH.sub.3                                                                          111-113                                        4.232 Cl   N(C.sub.2 H.sub.5)COCH.sub.2 Cl                                                                    98-101                                        4.233 Cl   N(C.sub.3 H.sub.7)COCH.sub.2 Cl                                                                   168                                            4.234 Cl   N(CH.sub.2 CH.sub.2 OCH.sub.3)COCH.sub.2 Cl                                                       107                                            4.235 Cl   N(CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5)COCH.sub.2 Cl                                                        1.54132 (20° C.)                4.236 Cl   N(CH.sub.2 Ph)COCH.sub.2 Cl                                                                       165-168                                        4.237 Cl   N(CH.sub.3)COCF.sub.3                                                                              98                                            4.238 Cl   N(C.sub.2 H.sub.5)COCF.sub.3                                                                      102                                            4.239 Cl   N(CH.sub.2CCH)COCF.sub.3                                                                          137                                            4.240 Cl   N(CH.sub.3)COC.sub.2 H.sub.5                                                                      125-128                                        4.241 Cl   N(C.sub.2 H.sub.5)COOC.sub.2 H.sub.5                                                               83                                            4.242 Cl   N(CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5)COC.sub.2 H.sub.5                                                    1.54132 (20° C.)                4.243 Cl   N(CH.sub.3)COC.sub.3 H.sub.7                                                                       90                                            4.244 Cl   N(C.sub.2 H.sub.5)COC.sub.3 H.sub.7                                                                72                                            4.245 Br   N(C.sub.2 H.sub.5)COC.sub.3 H.sub.7                                                               103-104                                        4.246 Cl                                                                                  ##STR153##         121                                            4.247 Cl                                                                                  ##STR154##         122                                            4.248 Cl                                                                                  ##STR155##         191                                            4.249 Cl   N(CH.sub.3)COOC.sub.4 H.sub.9                                                                             1.5427 (23.2° C.)               4.250 Cl   N(C.sub.2 H.sub.5)COOC.sub.4 H.sub.9                                                                      1.5386 (23.3° C.)               4.251 Cl   N(COCH.sub.3)CH.sub.2 OCH.sub.3                                                                   109                                            4.252 Cl   N[CH(CH.sub.3).sub.2 ]COCH.sub.3                                                                  112-114                                        4.253 Cl   N(CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5)COCH.sub.3                                                   100-103                                        4.254 Cl   N[CH(CH.sub.3)CH(CH.sub.3).sub.2 ]COCH.sub.3                                                       93                                            4.255 Cl   N[CH(CH.sub.3).sub.2 ]COCH.sub.2 Cl                                                               146-149                                        4.256 Cl   N[CH(CH.sub.3)C.sub.2 H.sub.5 ]COCH.sub.2 Cl                                                      109-111                                        4.257 Cl   N[CH(CH.sub.3)CH.sub.2 OCH.sub.3 ]COCH.sub.2 Cl                                                   126                                            4.258 Cl   N(CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5)COCH.sub.3                                                           1.5655 (22.4° C.)               __________________________________________________________________________    General formula                                                                ##STR156##                                                                   Example                        Physical Constant                              No.   R.sup.3 R.sup.6          mp: [°C.]                                                                        n.sub.D                              __________________________________________________________________________    4.259 Cl      N(CH.sub.3)COCH.sub.3                                                                          108-109                                        4.260 Cl      N(CH.sub.3)COCH.sub.2 Cl                                                                       87-90                                          4.261 Cl      N(CH.sub.3)COC.sub.2 H.sub.5                                                                   63-67                                          4.262 Cl      N(C.sub.2 H.sub.5)COCH.sub.3                                                                   77                                             4.263 Br      N(C.sub.2 H.sub.5)COC.sub.3 H.sub.7                                                            75-77                                          4.264 Cl      N(C.sub.3 H.sub.7)COCH.sub.3                                                                   78-80                                          4.265 Br      N(Et)COEt                  1.5168                               4.266 Br                                                                                     ##STR157##                1.51532                              4.267 Br                                                                                     ##STR158##                1.53406                              4.268 Br      N(CH.sub.2 CN)COEt                                                                             95-98                                          4.269 Br      N(Me)COC.sub.3 H.sub.7     1.55112                              4.270 Br      N(CH.sub.2 OCH.sub.3)COC.sub.3 H.sub.7                                                                   1.53024                              4.271 Br      N(CH.sub.2 CO.sub.2 Et)COC.sub.3 H.sub.7                                                                 1.52918                              __________________________________________________________________________    General formula                                                                ##STR159##                                                                   Example                      Physical Constant                                No.   R.sup.3                                                                             R.sup.6          mp: [°C.]                                                                       n.sub.D                                 __________________________________________________________________________    4.272 Cl    OCH.sub.3        174-176                                          4.273 Cl    OC.sub.2 H.sub.5 117-118                                          4.274 Br    OC.sub.2 H.sub.5 120-122                                          4.275 Cl    OC.sub.3 H.sub.7 95-96                                            4.276 Cl    OCH.sub.2 CH.sub.2 OCH.sub.3                                                                            1.55562 (20° C.)                 4.277 Cl    OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                         1.54220 (20° C.)                 4.278 Cl    OCH.sub.2CCH     123                                              4.279 Cl    OC.sub.4 H.sub.9 74-76                                            4.280 Cl                                                                                   ##STR160##       99.5-101.5                                      4.281 Cl                                                                                   ##STR161##      102-104                                          4.282 Cl                                                                                   ##STR162##               1.5575 (21.8° C.)                4.283 Cl                                                                                   ##STR163##               1.5520 (22° C.)                  4.284 Cl                                                                                   ##STR164##               1.5524 (21.8° C.)                4.285 Cl                                                                                   ##STR165##      67-70                                            4.286 Cl    OCH.sub.2 CH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                           1.5306 (20° C.)                  4.287 Cl                                                                                   ##STR166##      91-93                                            4.288 Cl                                                                                   ##STR167##               1.5544 (22.7° C.)                4.289 Cl    SCH.sub.2 COOCH(CH.sub.3).sub.2                                                                125                                              4.290 Cl                                                                                   ##STR168##               1.6136 (21.5° C.)                4.291 Cl    SCH.sub.3        128                                              4.292 Cl    SCH.sub.2 CH.sub.3                                                                              62                                              4.293 Cl    SCH(CH.sub.3).sub.2       1.5786 (21.8° C.)                4.294 Cl    SCH.sub.2CCH      94                                              4.295 Cl    SCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                                      1.5646 (22.5° C.)                4.296 Cl    SCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                                   1.5602 (21.8° C.)                4.297 Cl    SOCH.sub.3       163                                              4.298 Cl    SO.sub.2 CH.sub.3                                                                              229                                              4.299 Cl    OCH.sub.2 CH(CH.sub.3).sub.2                                                                   84-87                                            4.300 Cl    OCH.sub.2 CH(OC.sub.2 H.sub.5).sub.2                                                                    1.5283 (20° C.)                  4.301 Cl    O(CH.sub.2).sub.3 OCH.sub.3                                                                             1.5482 (20° C.)                  4.302 Cl    OCH.sub.2 Ph     120-122                                          4.303 Cl    OCH.sub.2 CH.sub.2 OCH(CH.sub.3).sub.2                                                         67-69                                            4.304 Cl                                                                                   ##STR169##      149-152                                          4.305 Cl    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                             4.306 Cl    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                4.307 Cl                                                                                   ##STR170##                                                       4.308 Cl                                                                                   ##STR171##                                                       4.309 Cl                                                                                   ##STR172##                                                       4.310 Cl                                                                                   ##STR173##                                                       4.311 Cl                                                                                   ##STR174##                                                       __________________________________________________________________________    General formula                                                                ##STR175##                                                                   Example                        Physical Constant                              No.   R.sup.6                  mp: [°C.]                                                                        n.sub.D                              __________________________________________________________________________    4.312 SCH.sub.2 CO.sub.2 Et    1.53242 (20.2° C.)                      4.313 SCH.sub.3                                                               4.314 SEt                                                                     4.315 Sprop                                                                   4.316                                                                                ##STR176##                                                             4.317 S nbutyl                                                                4.318                                                                                ##STR177##                                                             4.319                                                                                ##STR178##                                                             4.320 OCH.sub.3                                                               4.321 OEt                                                                     4.322 O prop                                                                  4.323                                                                                ##STR179##                                                             4.324 O nbutyl                                                                4.325                                                                                ##STR180##                                                             4.326                                                                                ##STR181##                                                             4.327                                                                                ##STR182##                                                             4.328                                                                                ##STR183##                                                             4.329                                                                                ##STR184##                                                             4.330                                                                                ##STR185##                                                             4.331                                                                                ##STR186##                                                             4.332                                                                                ##STR187##                                                             4.333                                                                                ##STR188##                                                             4.334                                                                                ##STR189##                                                             4.335                                                                                ##STR190##                                                             4.336                                                                                ##STR191##                                                             4.337                                                                                ##STR192##                                                             4.338                                                                                ##STR193##                                                             4.339                                                                                ##STR194##                                                             4.340                                                                                ##STR195##                                                             4.341                                                                                ##STR196##                                                             4.342                                                                                ##STR197##                                                             4.343                                                                                ##STR198##               98-100                                        4.344                                                                                ##STR199##              103-105                                        4.345                                                                                ##STR200##              93-96                                          4.346                                                                                ##STR201##                                                             4.347                                                                                ##STR202##                        1.51180                              4.348                                                                                ##STR203##              101-103                                        4.349                                                                                ##STR204##              105-108                                        4.350                                                                                ##STR205##              96-98                                          4.351                                                                                ##STR206##                                                             4.352                                                                                ##STR207##                                                             4.353                                                                                ##STR208##                                                             4.354                                                                                ##STR209##                                                             __________________________________________________________________________    General formula                                                                ##STR210##                                                                   Example                      Physical Constant                                No.   R.sup.5  R.sup.6       mp: [°C.]                                                                          n.sub.D                              __________________________________________________________________________    4.355 CN       N(C.sub.2 H.sub.5).sub.2                                                                    89-90                                            4.356 CN                                                                                      ##STR211##   123-124                                          4.357 CN       CH.sub.3                                                       4.358 CN       CH.sub.2 OCH.sub.3                                             4.359 CN       Br                                                             4.360 CN       Cl                                                             4.361 CN       OCH.sub.2 CH.sub.2 OCH.sub.3                                   4.362 NO.sub.2                                                                                ##STR212##                                                    __________________________________________________________________________

The following examples illustrate the possibilities for use of thecompounds of the invention.

In these Examples, herbicidal activity is denoted on a score of 0 to 4in which:

0=no damage

1=1-24% damage

2=25-74% damage

3=75-89% damage

4=90-100% damage

The abbreviations used for the various plant species have the followingmeanings

ABUTH=Abutilon theophrasti VERDE=Veronica persica

AGRRE=Elymus repens VIOSS=Viola sp

ALOMY=Alopecurus myosuroides

AVEFA=Avena fatua

BROTE=Bromus tectorum

CYPDI=Cyperus difformis

CYPES=Cyperus esculentus

ECHGH=Echinochloa crus-galli

GALAP=Galium aparine

GOSHI=Gossypium hirsutum

IPOSS=Ipomea purpurea

MATCH=Matricaria chamomilla

MOOVA=Monochoria vaginalis

ORYSA=Oryza satira

PANSS=Panicum maximum

PASDS=Paspalum distichum

POLSS=Polygonum sp.

SCPJU=Scirpus juncoides

SEBEX=Sesbania exaltata

SETVI=Setaria viridis

SORHA=Sorghum halepense

SOLSS=Solanum sp.

Test Example A

In a greenhouse, the noted plant species were treated pre-emergentlywith the noted compounds, at a rate of 0.1 kg active ingredient/ha. Thecompounds were sprayed evenly over the soil as emulsions in 500 litreswater/ha. Three weeks after the treatment, the compounds of theinvention showed excellent activity against the weeds. The comparisonmaterial did not show the same high activity.

    __________________________________________________________________________               A A A B S   P S C   A I M P S S V V                                           L G V R E   A O Y   B P A O E O E I                                           O R E O T   N R P   U O T L B L R O                                           M R F T V   S H E   T S C S E S P S                                           Y E A E I   S A S   H S H S X S E S                                __________________________________________________________________________    Ex. 1.1    --                                                                              --                                                                              --                                                                              --                                                                              3   3 3 --  3 --                                                                              4 2 1 4 3 4                                Ex. 1.2    3 --                                                                              3 --                                                                              4   4 --                                                                              --  4 3 4 4 4 4 4 4                                Ex. 1.6    3 3 3 --                                                                              4   4 3 --  4 --                                                                              4 4 3 4 4 4                                Ex. 1.7    --                                                                              --                                                                              --                                                                              --                                                                              3   3 3 --  4 --                                                                              4 3 4 4 4 2                                Ex. 1.8    2 --                                                                              --                                                                              --                                                                              2   2 3 --  4 --                                                                              4 4 3 4 3 2                                Ex. 1.9    2 2 3 --                                                                              4   3 3 --  4 --                                                                              4 3 3 4 4 4                                Ex. 1.11   2 --                                                                              3 --                                                                              4   3 3 --  3 --                                                                              4 1 0 4 4 3                                Ex. 1.13   3 --                                                                              3 --                                                                              4   3 4 2   4 --                                                                              4 4 3 4 4 2                                Ex. 1.15   3 2 2 --                                                                              4   4 2 --  --                                                                              --                                                                              4 2 2 4 3 4                                Ex. 1.18   4 3 3 --                                                                              4   4 4 3   4 --                                                                              4 4 2 4 4 4                                Ex. 2.1    3 4 4 4 4   4 4 3   4 4 4 4 4 4 4 4                                Ex. 2.11   3 --                                                                              3 --                                                                              --  4 4 4   3 4 4 4 4 4 4 4                                Ex. 2.12   3 --                                                                              3 --                                                                              4   4 4 --  4 3 4 4 4 4 4 4                                Ex. 2.13   3 --                                                                              --                                                                              --                                                                              4   4 4 --  3 3 4 4 4 3 4 4                                Ex. 2.17   3 3 3 --                                                                              4   4 4 --  4 4 4 4 4 4 4 4                                Ex. 2.18   3 --                                                                              3 --                                                                              4   4 3 --  4 --                                                                              4 4 2 4 4 4                                Ex. 2.24   3 --                                                                              3 --                                                                              3   3 3 3   4 4 3 4 4 4 4 3                                Ex. 2.38   3 --                                                                              --                                                                              --                                                                              3   3 --                                                                              --  4 3 4 3 4 4 4 4                                Ex. 4.12   4 4 4 3 4 4 4 3 4 4 4 4 4 4 4 4 4 4                                Untreated  0 0 0 0 0   0 0 0   0 0 0 0 0 0 0 0                                Comparison                                                                    5-tert-butyl-3-                                                                          0 0 0 1 2   4 0 0   1 1 3 1 0 3 2 3                                (2,4-dichloro-5-                                                              isopropoxyphenyl)-                                                            1,3,4-oxadiazol-2-one                                                         __________________________________________________________________________

Test Example B

In a greenhouse, the noted plant species were treated post-emergentlywith the noted compounds, at a rate of 0.3 kg active ingredient/ha. Thecompounds were sprayed evenly over the plants as emulsions in 500 litreswater/ha. Two weeks after the treatment, the compounds of the inventionshowed activity against the weeds. The comparison material did not showthe same high activity.

    __________________________________________________________________________               A A A B S P S C A G I M P S S V V                                             L G V R E A O Y B A P A O E O E I                                             O R E O T N R P U L O T L B L R O                                             M R F T V S H E T A S C S E S P S                                             Y E A E I S A S H P S H S X S E S                                  __________________________________________________________________________    Ex. 1.0    2 2 2 --                                                                              4 3 3 --                                                                              4 3 4 4 4 4 4 4 3                                  Ex. 1.1    3 3 3 --                                                                              4 3 3 --                                                                              4 3 3 4 4 4 4 4 3                                  Ex. 1.2    4 --                                                                              3 --                                                                              3 --                                                                              3 3 4 3 4 4 4 4 4 4 4                                  Ex. 1.6    4 3 3 2 4 3 3 3 4 3 4 4 4 4 4 4 4                                  Ex. 1.7    3 3 2 --                                                                              3 3 3 --                                                                              4 4 4 3 4 4 4 4 4                                  Ex. 1.8    3 3 3 --                                                                              3 3 3 3 4 3 4 3 4 4 4 4 4                                  Ex. 1.10   --                                                                              --                                                                              3 --                                                                              3 --                                                                              3 --                                                                              4 --                                                                              3 3 4 3 4 4 3                                  Ex. 1.12   --                                                                              --                                                                              --                                                                              --                                                                              3 2 3 --                                                                              4 --                                                                              3 2 4 3 4 3 3                                  Ex. 1.13   3 2 3 --                                                                              3 3 3 3 4 --                                                                              4 4 4 3 4 4 3                                  Ex. 1.18   3 3 3 3 4 3 3 3 4 4 4 4 4 4 4 4 3                                  Ex. 2.1    3 3 4 4 4 4 3 4 4 4 4 4 4 4 4 4 4                                  Ex. 2.11   3 3 3 --                                                                              4 4 4 --                                                                              4 4 4 4 4 4 4 4 4                                  Ex. 2.12   3 --                                                                              4 --                                                                              3 3 4 3 4 4 3 4 4 4 4 4 3                                  Ex. 2.13   3 --                                                                              3 --                                                                              3 --                                                                              3 3 4 3 4 4 4 4 4 4 3                                  Ex. 2.17   3 3 3 --                                                                              4 3 3 3 4 3 4 4 4 4 4 4 3                                  Ex. 2.18   3 --                                                                              3 --                                                                              3 3 3 3 4 3 3 4 4 4 4 4 3                                  Ex. 2.24   3 --                                                                              3 --                                                                              3 3 3 3 4 3 4 3 4 4 4 4 3                                  Ex. 2.38   --                                                                              3 --                                                                              --                                                                              3 3 --                                                                              --                                                                              4 3 3 4 3 4 4 4 4                                  Ex. 4.12   4 3 4 4 4 4 3 3 4 4 4 4 4 4 4 4 4                                  Untreated  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                  Comparison 0 1 1 0 1 0 1 1 4 2 3 2 3 2 4 1 3                                  5-tert-butyl-3-                                                               (2,4-dichloro-5-                                                              isopropoxyphenyl)-                                                            1,3,4-oxadiazol-2-one                                                         __________________________________________________________________________

Test Example C

In a greenhouse, the compounds noted in the table were applied at therates mentioned. For this the formulated active ingredients werepipetted onto the water surface

The test plants were treated pre-emergently and in the 1-3 leaf stage.

    ______________________________________                                                             O       E   C     S   M                                                       R       C   Y     C   O                                                       Y       H   P     P   O                                           Concentration                                                                             S       C   D     J   V                                  Compound kg/ha       A       G   I     U   A                                  ______________________________________                                        Ex. 1.0  0.04        0       2   4     1   4                                  Ex. 1.1  0.04        0       3   4     3   4                                  Ex. 1.17 0.1         0       --  4     --  4                                  Ex. 1.2  0.005       1       4   4     4   4                                  Ex. 1.4  0.05        1       3   4     2   4                                  Ex. 1.5  0.10        0       3   4     1   2                                  Ex. 1.6  0.04        1       4   4     4   4                                  Ex. 1.7  0.04        0       4   4     3   2                                  Ex. 1.8  0.04        0       4   4     4   4                                  Ex. 1.9  0.0125      0       3   4     3   4                                  Ex. 1.10 0.01        0       4   4     4   4                                  Ex. 1.11 0.05        1       4   4     4   4                                  Ex. 1.13 0.02        1       3   4     2   4                                  Ex. 1.14 0.02        0       4   4     2   4                                  Ex. 1.15 0.01        0       1   4     0   4                                  Ex. 1.18 0.01        2       4   4     3   4                                  Ex. 1.21 0.025       1       4   4     3   4                                  Ex. 1.22 0.05        1       4   4     2   4                                  Ex. 1.29 0.2         0       --  4     3   4                                  Ex. 1.36 0.04        1       4   4     3   4                                  Ex. 2.0  0.05        1       3   4     3   4                                  Ex. 2.1  0.01        1       4   4     4   4                                  Ex. 2.17 0.01        0       3   --    1   4                                  Ex. 2.18 0.01        1       3   4     2   4                                  Ex. 2.38 0.04        0       3   --    2   4                                  Ex. 3.3  0.08        1       4   4     4   4                                  Ex. 4.100                                                                              0.05        1       4   4     4   4                                  Ex. 4.101                                                                              0.05        1       4   3     3   4                                  Ex. 4.102                                                                              0.025       0       --  4     --  4                                  Ex. 4.103                                                                              0.01        0       --  --    --  4                                  Ex. 4.104                                                                              0.1         1       4   4     3   4                                  Ex. 4.105                                                                              0.05        1       4   4     4   4                                  Ex. 4.122                                                                              0.04        1       --  --    --  4                                  Ex. 4.125                                                                              0.025       0       4   4     4   4                                  Ex. 4.129                                                                              0.1         0       4   4     3   4                                  Ex. 4.130                                                                              0.025       1       4   4     3   4                                  Ex. 4.135                                                                              0.025       1       3   4     3   4                                  Ex. 4.137                                                                              0.1         0       3   --    --  4                                  Ex. 4.138                                                                              0.04        0       --  4     2   3                                  Ex. 4.140                                                                              0.04        0       4   4     3   4                                  Ex. 4.141                                                                              0.08        0       3   4     3   4                                  Ex. 4.143                                                                              0.08        0       3   4     3   4                                  Ex. 4.144                                                                              0.04        0       --  4     --  4                                  Ex. 4.146                                                                              0.2         0       4   4     3   4                                  Ex. 4.147                                                                              0.08        0       4   4     2   4                                  Ex. 4.148                                                                              0.08        0       4   4     2   4                                  Ex. 4.150                                                                              0.04        0       4   4     --  4                                  Ex. 4.151                                                                              0.04        0       --  4     --  3                                  Ex. 4.152                                                                              0.1         0       4   3     4   4                                  Ex. 4.153                                                                              0.1         0       4   4     3   4                                  Ex. 4.154                                                                              0.04        0       4   4     2   4                                  Ex. 4.155                                                                              0.04        1       4   4     2   4                                  Ex. 4.157                                                                              0.2         0       4   3     3   4                                  Ex. 4.158                                                                              0.1         0       4   4     4   4                                  Ex. 4.159                                                                              0.1         0       4   4     4   4                                  Ex. 4.164                                                                              0.05        0       4   4     4   4                                  Ex. 4.165                                                                              0.05        0       4   4     4   4                                  Ex. 4.166                                                                              0.05        1       4   4     4   4                                  Ex. 4.167                                                                              0.05        0       4   4     3   4                                  Ex. 4.168                                                                              0.05        0       4   4     3   4                                  Ex. 4.169                                                                              0.05        0       4   4     3   4                                  Ex. 4.177                                                                              0.08        0       4   4     4   4                                  Ex. 4.178                                                                              0.025       0       4   4     4   4                                  Ex. 4.179                                                                              0.1         1       3   4     3   4                                  Ex. 4.180                                                                              0.05        1       4   4     3   4                                  Ex. 4.185                                                                              0.1         1       3   4     2   4                                  Ex. 4.186                                                                              0.1         1       4   --    2   4                                  Ex. 4.187                                                                              0.005       --      3   3     2   3                                  Ex. 4.189                                                                              0.005       1       3   4     3   3                                  Ex. 4.191                                                                              0.02        1       4   4     --  4                                  Ex. 4.192                                                                              0.04        0       --  4     --  3                                  Ex. 4.194                                                                              0.05        1       --  --    3   4                                  Ex. 4.196                                                                              0.1         1       4   3     4   4                                  Ex. 4.197                                                                              0.1         1       4   4     4   4                                  Ex. 4.198                                                                              0.1         0       3   --    --  4                                  Ex. 4.2  0.025       0       4   --    4   4                                  Ex. 4.200                                                                              0.01        1       3   --    --  4                                  Ex. 4.205                                                                              0.025       1       4   --    4   4                                  Ex. 4.206                                                                              0.04        0       3   4     2   4                                  Ex. 4.206                                                                              0.04        0       3   4     2   4                                  Ex. 4.228                                                                              0.08        0       4   4     3   4                                  Ex. 4.230                                                                              0.08        1       3   4     2   4                                  Ex. 4.234                                                                              0.04        0       4   4     3   4                                  Ex. 4.26 0.025       0       4   4     3   4                                  Ex. 4.27 0.01        1       4   4     2   4                                  Ex. 4.227                                                                              0.1         1       3   2     3   4                                  Ex. 4.229                                                                              0.05        1       4   --    4   4                                  Ex. 4.231                                                                              0.1         0       3   --    --  4                                  Ex. 4.233                                                                              0.08        0       4   4     3   4                                  Ex. 4.235                                                                              0.02        1       3   4     --  4                                  Ex. 4.236                                                                              0.2         0       4   4     2   4                                  Ex. 4.237                                                                              0.04        0       3   4     3   4                                  Ex. 4.238                                                                              0.04        0       4   4     3   4                                  Ex. 4.239                                                                              0.04        0       4   4     4   4                                  Ex. 4.240                                                                              0.08        1       3   4     2   4                                  Ex. 4.241                                                                              0.04        0       3   4     2   4                                  Ex. 4.242                                                                              0.04        0       --  4     --  3                                  Ex. 4.243                                                                              0.08        0       2   4     2   4                                  Ex. 4.244                                                                              0.08        0       4   4     3   4                                  Ex. 4.245                                                                              0.08        0       3   4     2   4                                  Ex. 4.246                                                                              0.1         0       4   4     --  4                                  Ex. 4.247                                                                              0.1         0       4   4     3   4                                  Ex. 4.248                                                                              0.025       0       3   4     2   4                                  Ex. 4.25 0.05        1       4   4     3   4                                  Ex. 4.251                                                                              0.1         1       3   --    4   4                                  Ex. 4.252                                                                              0.05        0       --  3     --  --                                 Ex. 4.255                                                                              0.1         0       --  --    --  4                                  Ex. 4.257                                                                              0.1         0       3   3     --  4                                  Ex. 4.275                                                                              0.025       0       4   --    3   4                                  Ex. 4.276                                                                              0.005       1       4   4     3   4                                  Ex. 4.277                                                                              0.005       1       --  3     --  3                                  Ex. 4.280                                                                              0.1         1       --  3     --  4                                  Ex. 4.281                                                                              0.025       1       3   --    2   4                                  Ex. 4.288                                                                              0.2         0       --  4     --  4                                  Ex. 4.29 0.05        1       4   4     4   4                                  Ex. 4.290                                                                              0.1         0       3   4     2   4                                  Ex. 4.291                                                                              0.025       1       4   4     3   4                                  Ex. 4.292                                                                              0.1         0       4   4     3   4                                  Ex. 4.295                                                                              0.2         0       3   --    4   4                                  Ex. 4.31 0.1         0       3   4     3   4                                  Ex. 4.32 0.005       1       3   4     2   4                                  Ex. 4.33 0.005       1       --  --    --  4                                  Ex. 4.34 0.002       1       3   4     2   4                                  Ex. 4.35 0.005       1       4   4     4   4                                  Ex. 4.37 0.01        0       3   2     2   4                                  Ex. 4.38 0.025       1       --  --    --  4                                  Ex. 4.41 0.005       1       3   4     --  4                                  Ex. 4.42 0.02        1       4   4     3   4                                  Ex. 4.43 0.02        1       4   3     2   4                                  Ex. 4.49 0.25        1       --  3     --  4                                  Ex. 4.50 0.02        1       3   4     2   4                                  Ex. 4.56 0.1         1       3   4     2   4                                  Ex. 4.57 0.025       1       4   --    3   4                                  Ex. 4.58 0.05        0       4   4     3   4                                  Ex. 4.59 0.04        0       4   4     4   4                                  Ex. 4.60 0.1         0       4   4     4   4                                  Ex. 4.61 0.02        0       4   4     2   4                                  Ex. 4.62 0.04        0       4   4     2   4                                  Ex. 4.64 0.04        0       4   4     2   4                                  Ex. 4.65 0.005       0       3   4     3   4                                  Ex. 4.66 0.1         0       --  --    --  4                                  Ex. 4.67 0.1         0       --  --    --  4                                  Ex. 4.68 0.04        0       4   4     2   4                                  Ex. 4.69 0.01        0       4   4     2   4                                  Ex. 4.70 0.08        0       4   4     4   4                                  Ex. 4.71 0.08        0       3   4     3   4                                  Ex. 4.73 0.05        0       4   4     4   4                                  Ex. 4.74 0.08        0       4   4     3   4                                  Ex. 4.75 0.05        0       4   4     4   4                                  Ex. 4.76 0.04        0       3   4     2   4                                  Ex. 4.79 0.04        0       3   --    --  4                                  Ex. 4.80 0.04        1       4   --    3   4                                  Ex. 4.82 0.1         0       --  --    --  4                                  Ex. 4.83 0.1         0       1   4     4   4                                  Ex. 4.84 0.02        1       3   4     3   4                                  Ex. 4.85 0.025       0       4   4     3   4                                  Ex. 4.87 0.1         0       4   4     4   4                                  Ex. 4.88 0.1         0       4   4     2   4                                  Ex. 4.89 0.1         0       --  3     --  4                                  Ex. 4.90 0.025       0       3   --    --  4                                  Ex. 4.91 0.1         0       4   4     3   4                                  Ex. 4.92 0.05        1       4   4     4   4                                  Ex. 4.93 0.025       0       4   4     2   4                                  Ex. 4.94 0.1         0       --  --    3   4                                  Ex. 4.95 0.025       1       4   3     3   4                                  Ex. 4.96 0.005       0       3   4     2   4                                  Ex. 4.97 0.1         0       4   4     4   4                                  Ex. 4.98 0.05        1       4   4     3   4                                  Ex. 4.99 0.025       1       4   4     3   4                                  Untreated            0       0   0     0   0                                  ______________________________________                                    

As the table shows, the compounds of the invention show good activityagainst Echinochloa crus-galli (ECHGH) Cyperus difformis (CYPDI),Scirpus juncoides (SCPJU) and Monochoria vaginalis (MOOVA).

Example D

In a greenhouse, the noted plant species were treated with the notedcompounds, at a rate of 0.03 kg active ingredient/ha. The compounds weresprayed evenly over the plants as emulsions in 500 litres water/ha. Twoweeks after the treatment, the compounds of the invention showedexcellent activity against the weeds. The comparison material did notshow the same high activity.

    ______________________________________                                                 A     S     P   A   G   I   M   P   S   S   V                                                     V                                                                              L E A B A P A O E O E I                                                       O T N U L O T L B L R O                                                       M V S T A S C S E S P S                                                      Compound Y I S H P S H S X S E S                 ______________________________________                                        Ex. 3.1  3     4     4   4   3   4   4   4   4   4   4                                                     4                                                                             Untreated 0 0 0 0 0 0 0 0 0 0 0 0                                             Comparison                                                                    5-tert.-Butyl- 1 2 1 3 2 3 2 3 2 4 2 2                                        3-(2,4-                                                                       dichloro                                                                      isopropoxy-                                                                   phenyl)-1,3,4-                                                                oxadiazol-2-                                                                  one                                              ______________________________________                                    

Example E

In a greenhouse, the noted plant species were treated with the notedcompounds, at a rate of 0.1 kg active ingredient/ha. The compounds weresprayed evenly over the plants as emulsions in 500 litres water/ha. Twoweeks after the treatment, the compounds of the invention showedexcellent activity against the weeds. The comparison material did notshow the same high activity.

    __________________________________________________________________________               A A A B S P S C A G I M P S S V V                                             L G V R E A O Y B A P A O E O E I                                             O R E O T N R P U L O T L B L R O                                             M R F T V S H E T A S C S E S P S                                             Y E A E I S A S H P S H S X S E S                                  __________________________________________________________________________    Ex. 4.2    --                                                                              --                                                                              --                                                                              --                                                                              3 3 3 --                                                                              4 3 3 4 4 --                                                                              4 4 4                                  Ex. 4.3    3 --                                                                              3 3 4 4 3 --                                                                              4 4 4 4 4 4 4 4 3                                  Ex. 4.4    4 3 3 3 4 4 3 3 4 4 4 4 4 4 4 4 3                                  Untreated  0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                  Comparison                                                                    5-tert.-Butyl-3-                                                                         1 1 0 0 2 2 1 0 4 2 3 2 3 4 3 2 2                                  (2,4-dichloro-5-                                                              isopropoxyphenyl)-                                                            1,3,4-oxadiazol-2-one                                                         __________________________________________________________________________

We claim:
 1. A compound of the formula IIa ##STR213## in which R¹ is C₁-C₄ -alkyl; R² is C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkoxy, eachof which is optionally substituted by one or more halogen atoms; or R¹and R² together form the group --(CH₂)_(m) -- and m is 3 or
 4. 2.Substituted pyrazole derivative according to claim 1 in which R¹ ismethyl, R² is methylthio or difluoromethoxy, or R¹ and R² together formthe group --(CH₂)₄ --.
 3. Substituted pyrazole derivative according toclaim 2 in which R² is difluoromethoxy or together with R¹ forms thegroup --(CH₂)₄ --.